KR20160108608A - Oligomerization of alpha olefins using metallocene-ssa catalyst systems and use of the resultant polyalphaolefins to prepare lubricant blends - Google Patents

Abstract

The present invention provides alpha olefin oligomers and polyalphaolefins (or PAO) and alpha olefin oligomers and processes for making PAO. The present invention includes an activator comprising a solid oxide which comprises a metallocene-based alpha olefin oligomerization catalyst system and is chemically treated with at least one metallocene and an electron attracting anion. The alpha olefin oligomers and PAOs prepared with these catalyst systems have a high viscosity index and a low pour point, which is particularly useful as a viscosity modifier in lubricant compositions.

Description

METHODS FOR PRODUCING ALPHA OLEFINS USING METALLOCENE-SSA CATALYST SYSTEMS AND USE OF THE RESULTANT POLYALPHAOLEFINS TO PREPARE LUBRICANT BLENDS FOR THE PRODUCTION OF ALPHA OLEFINE OLIGOMERIZATION AND LUBRICANT BENDS USING METALLOCENE-

Cross reference of related applications

This application claims priority benefit of U.S. Provisional Patent Application No. 61 / 187,334, filed June 16, 2009, which is hereby incorporated by reference in its entirety.

TECHNICAL FIELD OF THE INVENTION

This disclosure relates to metallocene catalyzed oligomerization of alpha olefins to form alpha olefin oligomers and hydrogenation of poly alpha olefins, which are useful as synthetic lubricants and viscosity modifiers.

BACKGROUND OF THE INVENTION

Mono-1-olefins (alpha olefins), including ethylene, can sometimes be polymerized in a catalytic system employing titanium, zirconium, vanadium, chromium or other metals impregnated with various support materials in the presence of an activator. These catalyst systems are useful for both ethylene homopolymerization and copolymerization with ethylene and comonomers such as propylene, 1-butene, 1-hexene, or heavy alpha olefins. The need to develop new olefin polymerization catalysts, catalytic activation processes, and catalyst preparation and utilization methods that can provide new polymer materials suitable for improved catalytic activity, selectivity, or specific end use due to the importance of this process in the production of functional materials And continuous research.

One type of transition metal-based catalyst system employs a metallocene compound, sometimes in contact with an activating agent such as methylaluminoxane (MAO) to form an oligomerization catalyst. However, a large amount of expensive methylaluminoxane is typically required to form an active metallocene catalyst so as to obtain a desired degree of oligomerization activity. These features hinder commercialization of metallocene catalyst systems. Thus, there is a desire to improve the catalyst system and the catalyst preparation method which impart the desired oligomerization activity at a reasonable commercial cost. In addition, the development of catalysts that can provide polymers or oligomers with the desired properties that can be tailored and maintained to the desired specification remains a significant challenge.

SUMMARY OF THE INVENTION

The present invention provides alpha olefin oligomers, hydrogenated alpha olefin oligomers (also referred to as poly alpha olefins or PAO throughout the present invention), methods of making alpha olefin oligomers, methods of making hydrogenated alpha olefin oligomers, catalyst systems, and methods of making catalyst systems . In particular, the present invention provides alpha olefin homo oligomers (or homopolymers), hydrogenated alpha olefin homo oligomers, alpha olefinic co-oligomers (or copolymers) wherein the alpha olefin monomers do not include ethylene, or hydrogenated alpha olefin co oligomers. In metallocene-based olefin polymerization catalyst studies, when the metallocene and related catalytic components, metallocenes, when used with an activator consisting of a solid oxide chemically treated with an electron attracting anion, have a heavy alpha olefin (C ₃ or higher) It was found to be effective for oligomerization.

Alpha olefin oligomerization is accomplished by contacting the alpha olefin and the catalyst system, wherein the catalyst system is a metallocene-based system. In an embodiment, the catalyst system comprises a metallocene and an activator. In one embodiment, the activator comprises a solid oxide chemically treated with an electron attracting anion. In one embodiment, the activator may be an aluminoxane such as methyl aluminoxane (MAO) or methylated aluminoxane (MMAO). In another embodiment, the resulting hydrogenated alpha olefin oligomer has a high viscosity index; In contrast, it is characterized by high viscosity index and low pour point. This feature imparts these PAO availability particularly in lubricant compositions. In addition, the methods disclosed herein provide methods of modifying certain oligomerization or process parameters to control viscosity or select a range of viscosity. Another embodiment of the present invention provides PAOs comprising alpha olefin-derived monomer units, wherein the alpha olefin monomer does not substantially comprise 1-decene. It has been found that PAOs containing alpha olefin-derived monomer units that are substantially free of 1-decene do not need to be mixed with PAOs containing 1-decene-based monomer units to obtain PAOs having a high viscosity index and a low pour point. The economic advantages for the first-pass of such a process to provide a lubricant composition are obvious.

According to one aspect of the present invention there is provided an oligomerization process comprising:

a) Contacting the catalyst system comprising an alpha olefin monomer and at least one metallocene and a chemically-treated solid oxide; And

b) Lt; RTI ID = 0.0 > oligomerization < / RTI > production under oligomerization conditions.

According to one aspect of the present invention there is provided an oligomerization process comprising:

a) Alpha olefin monomers and

   One) At least one metallocene;

   2) At least one first activator comprising a chemically-treated solid oxide; And

   3) A catalyst system contacting step comprising at least one second activator; And

b) Lt; RTI ID = 0.0 > oligomerization < / RTI > production under oligomerization conditions.

In an embodiment, the chemically-treated solid oxide may be fluorinated silica-alumina. In an embodiment, the second activator may be an organoaluminum compound. In addition, the alpha olefin monomer and the catalyst system can be contacted by simultaneous contacting steps of an alpha olefin monomer, a metallocene, a first activator, and a second activator. Alternatively, the alpha olefin monomer and the catalyst system may be contacted in any order without limitation.

In one aspect, the present invention provides polyalphaolefins having a 100 < 0 > C kinematic viscosity of 20 cSt to 1,200 cSt. In another aspect, the present invention provides a polyalphaolefin having a pour point of less than -20 < 0 > C. In some embodiments, the present invention provides polyalphaolefins having a 100 ° C kinematic viscosity of 20 cSt to 270 cSt and a pour point of less than -30 ° C. Other useful properties such as Mw molecular weight, Mn molecular weight, polydispersity index, shear stability, crystal properties, stereoregularity, and Bernoulli's index (B) are described. In one embodiment, the PAOs disclosed herein may comprise primarily a head-to-tail oligomer. In an embodiment, the PAOs described herein may include a head-to-tail oligomer where less than 100 errors per 1000 alpha olefin monomers are present.

In one embodiment, the alpha olefinic monomers, singly or in combination, are C ₃ to C ₇₀ normal alpha olefins; But otherwise includes C ₄ to C ₂₀ normal alpha olefins. In an embodiment, the alpha olefin monomer may comprise 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, and any combination thereof.

Also provided is a lubricant composition comprising the polyalphaolefin composition produced by the present invention. The lubricant composition is substantially comprised of a PAO composition with or without additives such as metal deactivators, detergents, dispersants, antioxidants, and the like.

The present invention also provides a process for producing polyalphaolefins comprising:

a) contacting the catalyst system comprising an alpha olefin monomer, and a metallocene; And

b) forming an oligomer product under oligomerization conditions. The process for producing polyalphaolefins may also include separating the reactor effluent for production of the heavy oligomer product and hydrogenating the heavy oligomer product for polyalphaolefin production. The catalyst system may also comprise an activator or combination of activators; Alternatively, the catalyst system may be substantially devoid of activator. In some embodiments, the catalyst system may also include an activator. In some embodiments, the activator is selected from the group consisting of alumoxanes (e.g., methyl alumoxane or methyl alumoxane), trialkyl aluminum compounds, alkyl aluminum hydrides, alkyl aluminum halides, organozinc compounds, organomagnesium compounds, A lithium compound, an organic boron compound, an ionic ionic compound, a borate compound, or an aluminate compound, or any combination thereof.

In one embodiment, the activator may comprise a solid oxide chemically treated with an electron attracting anion. In some embodiments, the solid oxide chemically treated with an electron attracting anion may include fluorinated alumina, chlorinated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, fluorinated silica-zirconia, or combinations thereof . Accordingly, the present invention encompasses a process for producing polyalphaolefins comprising:

a) Alpha olefins,

Metallocenes; And

Contacting the catalyst system comprising an activator comprising a solid oxide chemically treated with an electron attracting anion; And

b) And forming an oligomer product under oligomerization conditions.

When a solid oxide chemically treated with an electron attracting anion is applied as an activator, it can be used alone or in combination with additional activators. Examples of activators that can be used in combination with the chemically-treated solid oxide include, but are not limited to, alumoxanes (e.g., methyl alumoxane or methyl alumoxane), trialkyl aluminum compounds, alkyl aluminum hydrides, An alkyl aluminum halide, an organozinc compound, an organomagnesium compound, an organolithium compound, an organoboron compound, an ionic ionic compound, a borate compound, or an aluminate compound, or any combination thereof.

Another aspect of the present invention provides a process for producing oligomeric products that can be further processed with polyalphaolefins wherein a combination of alpha olefin monomers, metallocenes, solid oxides, electron attracting anions, or any other activating agent Can be pre-contacted prior to their use in this catalytic treatment. In this embodiment, any pre-contacting step or steps may be performed for any period of time prior to the contacting step of the p-oligomerized alpha olefin and the alpha olefin oligomerization initiation catalyst system.

A wide variety of metallocene compounds may be suitably employed in the processes disclosed herein. The term "metallocene" as used herein is defined broadly as intended to include compounds containing at least one pi-bond eta ^{x 5} ligand. Generally, pi-bonded ligand is η ^{≥5 x} h ^{5-cyclopentadienyl,} h ^5-indenyl, h ^5-fluorenyl, h ^5-alkyne diene-yl -, or h ⁶ - borate benzene-ligand days . The pi-linkage [eta] ^{x > 5} ligand is also referred to as the I group ligand in the present invention. Thus, compounds containing only a single pi-bond eta ^{x > 5} ligand are encompassed by the term " metallocene "as used herein. In one embodiment, the metallocene metal may comprise a Group 4, 5, or Group 6 metal. Suitable metallocenes may include titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten. Any substituents or substituents on the pi-bonded ^< RTI ID ^{= 0.0} > eta ^< / RTI >< RTI ID = 0.0 > ⁵ ligands < / RTI > The metallocenes of the present invention also include Group II ligands, which are free of pi-linkage? ^X ? ⁵ ligands. Non-pi-bond η ^{x ≥5} ligand may include a single formal anionic ligands occupy a single coordination site in the metal. These single anionic ligands may include halides, hydrides, hydrocarbyl ligands, hydrocarboxy ligands, and amine ligands.

Suitable metallocenes may include those containing multiple ligands. In some embodiments, the ligands of the metallocene having multiple ligands may be non-crosslinked; Alternatively, the ligands of the metallocene with multiple ligands can be connected by a bridge. For example, a metallocene compound suitable for use in a catalyst system comprises a metallocene having two Group I ligands (pi-linkage? ^X ? ⁵ ligands) linked by a bridging group. Other suitable metallocenes include those in which a Group I ligand (pi-linkage? ^X ? ⁵ ligand) and a Group II ligand are linked by a bridging group.

The present invention also provides a novel catalyst system for the preparation of oligomeric products (which may be further treated with polyalphaolefins), a novel catalyst system preparation method, and an alpha olefin oligomerization process, The productivity can be improved without the need to use the activator excessively.

In addition, the present invention encompasses a process comprising contacting at least one monomer and a post-contacting catalyst system to produce an oligomer under oligomerization conditions. Accordingly, the present invention provides a method of oligomerization using a catalyst system prepared as described herein.

These and other embodiments and aspects of the alpha olefinic oligomer and oligomerization process are described in more detail and in the claims and in greater detail and are further disclosed herein.

1 shows the polyalphaolefin blend of the hydrogenated 1-octene oligomer according to the invention having a 100 DEG C kinematic viscosity of 38.8 cSt compared to commercially available 1-decene-derived PAO (PAO 40) having approximately the same kinematic viscosity. The kinematic viscosity (cP) versus temperature (C) plot. Samples: A , Blend B-2 , a blend of hydrogenated 1-octene oligomers having a kinematic viscosity of 100 cSt at 38.8 cSt; B , commercially available PAO 40. See Table 6 and 7 for sample preparation and properties.
Figure 2 shows the Brookfield mechanical viscosity (cP) of a polyalphaolefin blend of hydrogenated 1-octene oligomers with a kinematic viscosity of 99.3 cSt at 100 [deg.] C compared to commercially available PAO (PAO 100) ) Vs. temperature (C) plot. Samples: A , Blend B-3 , a blend of hydrogenated 1-octene oligomers having a kinematic viscosity of 100 cSt at 100 DEG C; B , commercially available PAO 100. See Table 6 and 7 for sample preparation and properties.
3 shows the oxidation stability RPVOT (rotational pressure vessel oxidation experiment) analysis result of hydrogenated 1-octene oligomer measured according to ASTM D2272. Oxidation stability plots of oxygen pressure (psig) versus time (min) showing comparative oxidation stability of hydrogenated 1-octene oligomers prepared using metallocene and chemically treated solid oxide catalyst systems compared to commercial PAO. Sample: A , blend B-2 , hydrogenated 1-octene oligomer blend having a 100 占 폚 kinematic viscosity of 38.8 cSt ; B , hydrogenated 1-octene oligomer (oligomer hydrogenation at 210 캜) having a 100 캜 kinematic viscosity of 121 cSt; C , hydrogenated 1-octene oligomer (oligomer hydrogenation at 165 캜) having a 100 캜 kinematic viscosity of 121 cSt; Commercially available PAO 40 produced in D , 1-decene; E , commercially available PAO 100 produced from 1-decene. See Table 6 and 7 for sample preparation and properties.
Figure 4 illustrates the metallocene effect of the oligomerization catalyst system on the 100 < 0 > C kinematic viscosity of the hydrogenated oligomers produced using the oligomerization catalyst systems and methods described herein. Figure 4 shows the kinematic viscosities (cP) versus temperature (占 폚) of a series of hydrogenated oligomers produced using different metallocene oligomerization catalyst systems and commercially available polyalphaolefins at 100 占 폚 kinematic viscosity of 40 cSt. Sample A : Hydrogenated 1-decene oligomer having a kinematic viscosity of 41 cSt at 100 DEG C, prepared using metallocene J (Example 8 - Run 5); B , hydrogenated 1-octene oligomer with a kinematic viscosity of 43.8 cSt at 100 DEG C, prepared using metallocene N (Example 8 - Run 6); C , hydrogenated 1-octene oligomer with a kinematic viscosity of 37 cSt at 100 占 폚 produced by applying metallocene L (Example 8 - Run 7); D , commercially available PAO 40; E , a blend B-2 , a hydrogenated 1-octene oligomer blend having a 100 占 폚 kinematic viscosity of 38.8 cSt. Refer to Tables 6 and 7 for sample preparation and characteristics.
Figure 5 illustrates the metallocene effect of the oligomerization catalyst system on the 100 < 0 > C kinematic viscosity of hydrogenated oligomers produced using the oligomerization catalyst systems and methods described herein. Figure 5 shows the kinematic viscosities (cP) versus temperature (占 폚) of a series of hydrogenated oligomers produced using different metallocene oligomerization catalyst systems and commercially available polyalphaolefins having a 100 ° C kinematic viscosity of 100 cSt. Sample: A hydrogenated 1-octene oligomer having a kinematic viscosity of 118 cSt at 100 DEG C prepared using metallocene J (Example 8 - Run 10); B , hydrogenated 1-decene oligomer having a kinematic viscosity of 100.5 cSt at 100 DEG C, prepared using metallocene J (Example 8 - Run 11); C , hydrogenated 1-octene oligomer having a kinematic viscosity of 112.8 占 폚 43.8 cSt, prepared by applying metallocene B (Example 8 - Run 12); D , commercially available PAO 100. See Table 6 and 7 for sample preparation and properties.
6 is DSC of PAO prepared using 1-octene according to Example 8-Run 6. The DSC shows that there is no discernible crystallization according to the DSC method described herein.
7 is DSC of PAO prepared using 1-decene according to Example 8-Run 5. The DSC shows that there is no discernible crystallization according to the DSC method described herein.
8 is DSC of PAO prepared using 1-octene according to Example 8-Run 10. The DSC shows that there is no discernible crystallization according to the DSC method described herein.
9 is DSC of PAO prepared using 1-decene according to Example 8-Run 11. According to the DSC, there is some discernible crystallization according to the DSC method described herein.
10 is DSC of PAO prepared using 1-octene according to Example 8-Run 12. The DSC shows that there is no discernible crystallization according to the DSC method described herein.
Figure 11 is the DSC of a commercial PAO. According to DSC, there is an identifiable crystallization according to the DSC method described herein.

DETAILED DESCRIPTION OF THE INVENTION

A comprehensive description

The present invention relates to a process for preparing an alpha olefin oligomer (also referred to as alpha olefin oligomer), a hydrogenated oligomer (also referred to as poly alpha olefin or PAO throughout), an alpha olefin oligomer preparation process, a PAO production process, a catalyst system, to provide. In particular, the present invention encompasses the oligomerization of one or more alpha olefins using a metallocene-containing catalyst system. The catalyst system further comprises one or more activators. One type of activator that may be particularly useful is a solid oxide chemically-treated with an electron attracting anion and is described in detail herein. The solid oxide chemically treated with an electron attracting anion is also referred to herein as a chemically treated solid oxide (CTSO), solid superacid (SSA), or activator-support, and these terms are used interchangeably . Other activators may be used in the catalyst system, together with the metallocene, alone or in combination with SSA, or in combination with at least one other activator. Thus, according to an embodiment, the catalyst system comprises at least one metallocene, a first activator, and a second activator. In one embodiment, the first activator comprises a chemically-treated solid oxide, or may be substantially comprised of or consist of a solid oxide, and the second activator comprises an organoaluminum compound or is substantially comprised of an organoaluminum compound Or may be accomplished. In a non-limiting embodiment, the chemically-treated solid oxide is fluorinated silica-alumina and the second activator is a trialkylaluminum compound such as triethylaluminum and / or triisobutylaluminum.

These metallocene-based alpha olefin oligomerization provides olefin oligomers and ultimately polyalphaolefins with particularly useful properties. Metallocene-based alpha olefinic oligomerization enables, among other things, the characterization of oligomers and PAOs based on the catalyst system and / or oligomerization conditions above all other factors described herein. For example, certain characteristics of the 1-octene homo oligomer produced by the present invention and the PAO produced by the homo-oligomer hydrogenation can be selected by adjusting the oligomerization run temperature. In addition, the product viscosity and pour point can be controlled by this adjustment, so that a high number of PAOs having a 100 ° C kinematic viscosity of 100 cSt and / or 40 cSt can be produced.

Justice

The following definitions are provided to clearly define the terms used herein. Unless otherwise indicated, the following definitions apply to this specification. Unless specifically defined herein and as used herein, the IUPAC Chemistry Dictionary, Second Edition (1997), unless conflicted with any other disclosure that applies to the present application, and which, when applied, Can be applied. The definitions or usages provided herein should in no way be contrary to the definitions or usages provided herein and the definitions or usages provided herein, with reference to any of the references contained herein.

The terms "comprising" and "comprising" are used interchangeably with the word "comprising" or "consisting of" and are inclusive or expansive and include additional, non-mentioned elements or methods Steps are not excluded. The term "comprising" excludes any element, step, or ingredient that is not specified in the claims. The term " practically occurring "is intended to limit the claims to those that do not materially affect the fundamental and novel characteristic (s) of the particular material or stage and claimed invention. A "substantial" claim is located between the closed claims set forth in the "done" form and the fully open claims set forth in the form of "comprising ". Unless otherwise indicated, the term "substantially" when describing a compound or composition may not be construed as including the term "comprising" but may include materials that do not materially alter the composition or method to which the term applies It is intended to describe the mentioned element. For example, the feedstock that is substantially made up of the feedstock A may comprise impurities typically present in commercially available or commercially available compounds or composition samples. It will be understood that when a claim comprises, consists, substantially consists of, and / or comprises a feature and / or feature subcategory (e.g., a method step, a feedstock feature, and / Transitional words apply only to the feature (s) in which they are used and it is possible to process different features within a claim into different transitions or transition clauses. For example, the method may include several stated steps (and other non-mentioned steps), but employs a catalyst system manufacturing method comprising specific steps and includes the recited elements and other non-recited elements Can be used. Although the compositions and methods are described as "comprising " various elements or steps, it is also possible that the compositions and methods are" consisting of "

Unless specifically stated to the contrary, "a," "an," and "the" are intended to include plural forms, eg, at least one. By way of example, what is specifically disclosed as being "a metallocene" encompasses a single metallocene, or a mixture or combination exceeding one metallocene.

Periodic element families are denoted using the numbering system indicated in the Periodic Table of the Elements published in Chemical and Engineering News , 63 (5), 27, 1985. In some instances, the element families may be denoted using the generic name assigned to the family; For example, Group 1 elements are alkali metals, Group 2 elements are alkaline earth metals, Group 3-12 elements are transition metals, and Group 17 elements are halogens or halides.

For any of the compounds described herein, unless otherwise indicated, the general structure or designation presented is intended to encompass all structural isomers, stereoisomers, and stereoisomers that may be generated by a particular arrangement of substituents. Thus, in a generic reference to a compound, unless otherwise expressly indicated, includes all structural isomers; Examples of pentane include n-pentane, 2-methyl-butane, and 2,2-dimethylpropane. In addition, reference to a generic formula or name includes all enantiomers, diastereomers, and other optical isomers, as well as enantiomeric or racemic forms, as well as stereoisomeric mixtures, as the text allows or requires in the text. For any particular structure or name presented, any general structure or designation presented also includes all stereoisomers, positional isomers, and stereoisomers that may be generated by a particular arrangement of substituents.

In one embodiment, a chemical "group" refers to a compound derived from a formal reference or "parent " compound, for example, formally Can be defined or described according to the number of hydrogen atoms removed from the parent compound. These groups may be substituted, coordinated or bonded to the metal atoms. By way of example, "alkyl group" is formed by formally removing one hydrogen atom from an alkane, and "alkylene group " is formally formed by removing two hydrogen atoms from an alkane. Further, more generic terms are used to encompass various groups formed by formally removing any ("one or more") hydrogen atoms from the parent compound and are referred to in this example as "alkane groups"Quot;,"alkylene group ", and materials in which three or more hydrogen atoms necessary for substitution have been removed from the alkane. Throughout this description, the ability of a substituent, ligand, or other chemical moiety to constitute a particular "to, " means that the group is followed by known chemical and structural principles when described. For example, the equation (eta -5-C ₅ H _{5) 2} is the metallocene compound having a Zr (CH ₃₎ (X) are described, X is a "group,""alkylene," or "alkane group" It is subject to the general principles of valence and bonding. When a gig is derived from ","derived from, "," formed by ", or "formed from ", these terms are used in their ordinary sense and may be used in any other context, But does not take into account the particular synthesis method of < RTI ID = 0.0 > Throughout the conjugation nomenclature, "eta- ⁵ " can be described as "η ⁵ -".

Many groups, such as "oxygen-bonding groups ", also referred to as" oxygen groups "are specified depending on the atoms that are attached to the metal or other chemical moiety as substituents. For example, the oxygen-linking group may be a hydrocarboxy (-OR where R is a hydrocarbyl group), an alkoxide (-OR where R is an alkyl group), a aryloxid (-OAr excitation In which Ar is an aryl group), or substituted analogues thereof. Also, unless otherwise specified, carbon-containing groups in which the number of carbon atoms is not specified may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 , 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 carbon atoms, Range. For example, unless otherwise specified, any carbon-containing group may contain 1 to 30 carbon atoms, 1 to 25 carbon atoms, 1 to 20 carbon atoms, 1 to 15 carbon atoms, 1 to 10 carbon atoms , Or 1 to 5 carbon atoms, and the like. In addition, other identifiers or quantitative terms may be used to indicate the presence or absence of a particular substituent, a particular site chemistry and / or stereochemistry, or a branched structure or a main chain.

When the term "substituted" is used to describe a group, for example, when referring to a substituted analog of a particular group, any non-hydrogen residues that formally replace the hydrogen in this group are described non-limitingly . Groups or groups may be referred to as "unsubstituted" or the equivalent term "non-substituted", which refers to the original group in which the non-hydrogen moiety does not replace the hydrogen in this group. "Substituted" includes, but is not limited to, inorganic substituents or organic substituents understood by those of ordinary skill in the art.

 The term "alpha olefinic oligomer (s)," "alpha olefin oligomer product (s)," "oligomer product (s)," or "oligomerization product (s)", and similar terms refer to alpha olefinic dimer , ≪ / RTI > and heavy alpha olefin oligomers. In general, the terms alpha alpha olefin dimer, alpha olefin trimer, and heavy alpha olefin oligomer (also referred to as dimer, trimer, or heavy oligomer, respectively) refer to an oligomer having two, three, or four alpha olefin monomer- Quot; refers to the products of oxidation. In any dimer, trimer, and heavy alpha olefin oligomer, the alpha olefin monomer units may be the same or different. Preparation of Oligomeric Products Exiting the Oligomerization Reactor Oligomeric products in combination with residual monomers and any other materials are referred to as "oligomerization reactor effluents "," reactor effluents ", or similar terms. Typically, alpha olefin oligomers and these terms describe the oligomer product included in the reactor effluent and the term " heavy oligomer product "is used to describe the distillation-post oligomer product. In any case, it is possible to determine whether the product is distilled in contextual and experimental contexts. Alpha olefinic oligomers and heavy oligomeric products and similar terms generally do not refer to post-hydrogenation samples, in which case the term polyalphaolefin (PAO) is used to define hydrogenated alpha olefin oligomers. (S), "" oligomerization product (s)," "alpha olefin oligomer (s)," Can contain up to 1% by weight of residual alpha olefinic monomers when referring to the olefinic oligomer product (s), "alpha olefin oligomer product (s), "," oligomer product (s), & . However, the residual alpha olefin monomer content can be specified to be less than 1% by weight. Also, terms such as "alpha olefin oligomer" or "oligomer product" when applied to a single carbon number of alpha olefin oligomers may also be referred to using the terms "alpha olefin homo oligomer "," homo oligomer product, Can be described. &Quot; Alpha olefin homo oligomers, "" homo oligomer products," and the like refer to other alpha olefins that are typically formed in any particular commercial sample of single alpha olefin monomers and have an impurity content that is not removed in the production of a single carbon number of alpha olefins, Other olefins, and other materials.

 A "heavy oligomer product" is a product in which some of the lower alpha olefin oligomers are removed from the oligomer product in the oligomerization reactor effluent. In one embodiment, the process of removing some lower alpha olefin oligomers is distillation. In other embodiments, the process of removing some lower alpha olefin oligomers may be purging or sparging. In another embodiment, the process of removing some lower alpha olefin oligomers may be distillation using gas purge. When the distillation, discharge, or injection material comprises some alpha olefin monomers (e.g., an oligomerization reactor effluent where all the alpha olefin monomer is not converted to the oligomer product), the distillation, Can be removed. Eventually, depending on the oligomerization process and the classification method, the heavy oligomer product may contain some less than alpha-olefin monomers (e.g., less than 1% by weight). Generally, some lower alpha olefin oligomer removal processes remove at least the alpha olefin monomer, dimer, and / or trimer portion to form a heavy oligomer product. It should be understood that the method for removing some lower alpha-olefin oligomers may characteristically remove some of the heavy olefin oligomers, but this does not undermine the intention to remove some of the lower alpha olefin oligomers. In some cases, the term alpha olefin oligomer can be used to describe the reaction products of both before and after distillation, and in this case, the distillation of the product can be confirmed by referring to the context and the experimental conditions.

 A "polyalphaolefin" (PAO) is a hydrogenated (or otherwise, substantially saturated) oligomer mixture and comprises units derived from alpha olefin monomers (ie alpha olefin oligomers). Unless otherwise specified, PAOs comprise units derived from alpha olefin monomer units, which can be the same (hydrogenated or substantially saturated alpha olefin homo oligomers) or different (hydrogenated or substantially saturated alpha olefinic co-oligomers) have. It will be appreciated by those skilled in the art that, depending on the process applied to the production of PAO, the as-produced alpha olefin oligomer may already be substantially saturated. For example, an ongoing process in the presence of hydrogen can produce an olefin oligomer that requires or does not require a separate hydrogenation step to provide a product with the desired properties. Generally, the alpha olefin monomers used to produce the polyalphaolefins may be any of the alpha olefin monomers described herein. One skilled in the art will recognize that the PAO production process (s) can leave some hydrogenated monomers in the PAO and the hydrogenated monomer content can be specified (e.g., less than 1% by weight).

The term "organyl group" is used herein as defined by IUPAC: an organic substituent independent of the type of action having one free valence on a carbon atom. Similarly, "organylene group" is an organic group independent of the type of action in which two hydrogen atoms are removed from an organic compound, and two hydrogen atoms are bonded to one carbon atom or one hydrogen atom to two different carbon atoms Can be removed from each. "Organic" refers to a generic group formed by removing one or more hydrogen atoms from carbon atoms. Thus, the terms "organyl group,""organganylenegroup," and "organic group" may have an organic functional group (s) and / or an atom (s) other than carbon and hydrogen, And / or atoms. By way of example, non-limiting examples of atoms other than carbon and hydrogen include halogen, oxygen, nitrogen, phosphorus, and the like. Non-limiting examples of functional groups include ethers, aldehydes, ketones, esters, sulfides, amines, and phosphines, and the like. In one embodiment, the hydrogen atom (s) removed in the "organyl group,""organganylenegroup," or "organic group" is replaced by a functional group such as an acyl group (-C (O) (-C (O) H), a carboxy group (-C (O) OH), a hydrocarboxycarbonyl group (-C (O) OR), a cyano group _2), N - hydrocarbyl carbamoyl group (-C (O) NHR), or N, N '- di-hydrocarbyl carbamoyl group may be bonded to a carbon atom of the group (-C (O) NR ₂₎ . In another aspect, "Organic group,""Organic carbonyl group," or "(s) a hydrogen atom removed from the organic group" is, for example, away from it, does not belong to the functional _{group, -CH 2 C (O) CH} 3 , -CH ₂ NR ₂ , and the like. An "organyl group,"" organganylene group, "or" organic group "may be aliphatic, including cyclic or acyclic, or aromatic. The terms "organyl group,""organganylenegroup," and "organic group" also encompass heteroatom-containing rings, heteroatom-containing rings, heteroaromatic rings, and heteroaromatic rings. The term "organyl group,""organganylenegroup," and "organic group" may be linear or branched unless otherwise specified. Finally, the definition of "organyl group,""organganylenegroup," or "organic group" includes definitions such as "hydrocarbyl group,""hydrocarbylenegroup,""hydrocarbongroup"Quot; alkyl ","alkylene group ",and" alkane group " When bonded to a transition metal, an "organyl group,""organganylenegroup," or "organic group" can also be described according to the conventional η ^x (eta-x) nomenclature, For example, an integer corresponding to the number of coordinated atoms according to the 18-electron rule.

The term "hydrocarbon" as used in the specification and claims refers to compounds having only carbon and hydrogen. Other identifiers may be used to indicate the presence of a particular group in the hydrocarbon (e.g., the halogenated hydrocarbon indicates the presence of one or more halogen atoms replacing an equivalent number of hydrogen atoms in the hydrocarbon). The term "hydrocarbyl group" is used herein in accordance with the IUPAC definition: a monovalent group formed by hydrogen atom removal in a hydrocarbon (i.e., a group having only carbon and hydrogen). Non-limiting examples of hydrocarbyl groups include ethyl, phenyl, tolyl, propenyl, and the like. Likewise, "hydrocarbylene group" refers to a group formed by the removal of two hydrogen atoms from a hydrocarbon, and two hydrogen atoms may be removed at one carbon atom or at two carbon atoms where one hydrogen atom is different. Thus, in accordance with the nomenclature used herein, "hydrocarbon group" means a general group formed by removal of one or more hydrogen atoms from a hydrocarbon (as needed for a particular group). The "hydrocarbyl group,""hydrocarbylenegroup," and "hydrocarbon group" may be aliphatic or aromatic, acyclic or cyclic groups, and / or may be linear or branched. The "hydrocarbyl group,""hydrocarbylenegroup," and "hydrocarbon group" may include rings, cyclic groups, aromatic rings, and aromatic ring systems having only carbon and hydrogen. Hydrocarbyl group, "" hydrocarbylene group," and "hydrocarbon group" may also be described according to the conventional η ^x (etha-x) nomenclature, where x is the transition metal Or an integer corresponding to the number of coordinated atoms predicted, for example, according to the 18-electron rule. The term "hydrocarbyl group,"" hydrocarbylene group, "and" hydrocarbon group ", as each member, Alkylene, cycloalkane group, aralkyl, aralkylene, and aralkane groups.

The aliphatic compound is a non-cyclic or cyclic, saturated or unsaturated carbon compound group except an aromatic compound. An "aliphatic group" is a general group formed by removing one or more hydrogen atoms from a carbon atom of an aliphatic compound (depending on the particular group, as needed). That is, the aliphatic compound is a non-aromatic organic compound. The aliphatic and thus aliphatic groups have an organic functional group (s) and / or an atom (s) other than carbon and hydrogen.

The term "alkane" as used herein and in the claims refers to a saturated hydrocarbon compound. Other identifiers may be used to indicate the presence of a particular group in the alkane (e.g., a halogenated alkane represents the presence of one or more halogen atoms replacing an equivalent number of hydrogen atoms in the alkane). The term "alkyl group" is used herein in accordance with the IUPAC definition: a monovalent group formed by hydrogen atom removal in an alkane. Similarly, "alkylene group" means a group formed by removal of two hydrogen atoms in an alkane (two hydrogen atoms at one carbon atom, or one hydrogen atom at two different carbon atoms). An "alkane group" is a generic term meaning a group formed by the removal of one or more hydrogen atoms in an alkane (depending on the particular group, as needed). Unless otherwise specified, the terms "alkyl group,""alkylenegroup," and "alkane group" may be non-cyclic or cyclic groups, and / or may be linear or branched. The primary, secondary, and tertiary alkyl groups are each derived by removing hydrogen atoms from the primary, secondary, and tertiary carbon atoms of the alkane. The n-alkyl group is derived by removing the hydrogen atom from the terminal carbon atom of the linear alkane. RCH ₂ (R ≠ H), R ₂ CH (R ≠ H), and R ₃ C (R ≠ H) groups are primary, secondary, and tertiary alkyl groups, respectively.

Cycloalkanes are, for example, saturated cyclic hydrocarbons with or without side chains such as cyclobutane. Other identifiers may be used to indicate the presence of a particular group in the cycloalkane (e.g., a halogenated cycloalkane indicates the presence of one or more halogen atoms replacing an equivalent number of hydrogen atoms in the cycloalkane). Each of the unsaturated cyclic hydrocarbons having one inward ring double bond or triple bond is referred to as a cycloalkene and a cycloalkene, respectively. Those having at least one such multiple bond are cycloalkadiene, cycloalkatriene, and the like. Other identifiers may be used to indicate the presence of a particular group in a cycloalkene, cycloalkadiene, cycloalkatriene, and the like.

 Is a monovalent group derived by removing a hydrogen atom from a ring carbon atom in a "cycloalkyl group" cycloalkane. For example, 1-methylcyclopropyl group and 2-methylcyclopropyl group are exemplified as follows.

Similarly, a "cycloalkylene group" is a group derived by the removal of two hydrogen atoms from a cycloalkane, at least one of which is removed from the ring carbon. Thus, a "cycloalkylene group" means a group derived from a cycloalkane in which two hydrogen atoms are formally removed at the same ring carbon to form a cycloalkane, or two hydrogen atoms are formally removed from two different ring carbons, and Include those groups in which the first hydrogen atom is formally removed at the ring carbon and the second hydrogen atom is formally removed at the carbon atom, i.e., the non-ring carbon atom, resulting in the cycloalkane. "Cycloalkane group" means a general group formed by the removal of one or more hydrogen atoms in a cycloalkane (as required and according to the specified group and at least one ring carbon).

The term "alkene" as used herein and in the claims is a linear or branched hydrocarbon olefin having one carbon-carbon double bond and the general formula C _n H _2n . The alkadienes are linear or branched hydrocarbon olefins and have two carbon-carbon double bonds and the general formula C _n H _2n-2 , wherein the alkatriene is a linear or branched hydrocarbon olefin and has three carbon- C _n H _{2n - 4} . Alkenes, alkadienes, and alkatrienes may be further identified by their carbon-carbon double bond (s) positions. Other identifiers may be used to indicate the presence or absence of specific groups in the alkene, alkadiene, or alkatriene. For example, a haloalkene means an alkene in which at least one hydrogen atom of the alkene has been replaced with a halogen atom.

An "alkenyl group" is a monovalent group derived from an alkene by removing a hydrogen atom from any carbon atom of the alkene. Thus, an "alkenyl group" includes groups in which a hydrogen atom is formally removed from an sp ² hybrid (olefinic) carbon atom and groups in which a hydrogen atom is formally removed from any other carbon atom. For one example, and unless otherwise specified, 1-propenyl (-CH = CHCH _3), 2- propenyl, _{[(CH 3) C = CH} 2], and 3-propenyl (-CH ₂ CH = CH ₂ ) Groups are included in the term "alkenyl group ". Similarly, "alkenylene group" means a group formed by the formal removal of two hydrogen atoms in an alkene, wherein two hydrogen atoms are removed at one carbon atom, or one hydrogen atom is removed at two different carbon atoms . "Alkenyi" means a general group formed by removing one or more hydrogen atoms in an alkene (depending on the particular group, as needed). When a hydrogen atom is removed from a carbon atom in a carbon-carbon double bond, both the position chemistry of the carbon from which the hydrogen atom is removed and the position chemistry of the carbon-carbon double bond can be specified. Other identifiers may be used to indicate the presence of specific groups in the alkenyl sequence. Alkenic groups can be further identified by their carbon-carbon double bond positions.

The term "alkyne" as used in the specification and claims is a linear or branched hydrocarbon olefin and has one carbon-carbon triple bond and the general formula C _n H _{2n - 2} . The alkadine is a hydrocarbon olefin having two carbon-carbon double bonds and the general formula C _n H _{2n -6} , and the alkatriene is a hydrocarbon olefin having three carbon-carbon triple bonds and a general formula C _n H _{2n -10 .} Alkynes, alkadienes, and alkatrients can be further identified by the carbon-carbon triple bond (s) position. Other identifiers may be used to indicate the presence or absence of specific groups in the alkene, alkadiene, or alkatriene. For example, haloalkyne means an alkyne in which one or more hydrogen atoms have been replaced with a halogen atom.

An "alkynyl group" is a monovalent group derived from an alkyne by removing a hydrogen atom from the carbon atom of the alkyne. Thus, an "alkynyl group" includes groups in which a hydrogen atom is formally removed from a sp-hybrid (acetylenic) carbon atom and groups in which a hydrogen atom is formally removed from any other carbon atom. For example and unless otherwise specified, the 1-propynyl (-C≡CH ₃ ) and 3-propinyl (HC≡CH ₂ -) groups are all included in the term "alkynyl". Similarly, "alkynylene group" is a group formed by the formal elimination of two hydrogen atoms in an alkyne, where two hydrogen atoms, if possible, at one carbon atom or one hydrogen atom at two different carbon atoms Can be removed. "Alkyn group" means a general group formed by eliminating one or more hydrogen atoms in alkyne (depending on the specific group, as needed). Other identifiers may be used to indicate the presence or absence of specific units in the nucleotide sequence. The alkyne group can be further identified by the carbon-carbon triple bond position.

The term "olefin " as used in the specification and claims means a compound having at least one carbon-carbon double bond that is not part of an aromatic ring or ring system. The term "olefin" includes aliphatic, aromatic, cyclic or acyclic, and / or linear and branched compounds having at least one carbon-carbon double bond that is not an aromatic ring or ring moiety unless otherwise specified . The term "olefin" by itself does not denote the presence and / or absence of heteroatoms and / or other carbon-carbon double bonds, unless expressly indicated otherwise. The olefin can be further identified by its carbon-carbon double bond position. It should be understood that alkenes, alkadienes, alkatrienes, cycloalkenes, and cycloalkadienes are members of the olefin family. The olefin can be further identified by the carbon-carbon double bond (s) position.

The term "alpha olefin " as used herein and in the claims means an olefin having a double bond between the first and second carbon atoms of the carbon atoms continuous chain. The term "alpha olefin" includes both linear and branched alpha olefins unless explicitly stated otherwise. In the case of branched alpha olefins, the branch may be at the 2-position (vinylidene) and / or the 3-position with respect to the olefinic double bond. The term "vinylidene" as used in the specification and claims means an alpha olefin having a branch at the 2-position relative to the olefinic double bond. The term "alpha olefin" by itself does not denote the presence and / or absence of heteroatoms and / or other carbon-carbon double bonds, unless expressly indicated otherwise. The term " hydrocarbon alpha olefin "or" alpha olefin hydrocarbon "means an alpha olefin compound containing only hydrogen and carbon.

The term "linear alpha olefin " as used herein means a linear olefin having a double bond between the first and second carbon atoms. The term "linear alpha olefin" by itself does not indicate the presence and / or absence of heteroatoms and / or other carbon-carbon double bonds, unless expressly indicated otherwise. The term " linear hydrocarbon alpha olefin "or" linear alpha olefin hydrocarbon "means a linear alpha olefin compound containing only hydrogen and carbon

The term "normal alpha olefin" as used in the specification and claims means a linear hydrocarbon mono-olefin having a double bond between the first and second carbon atoms. It is to be understood that "normal alpha olefins" are not synonymous with "linear alpha olefins ", and the term" linear alpha olefins "refers to linear aliphatic olefins having a double bond between the first and second carbon atoms and / Olefinic compounds.

As used herein and in the claims, the term " consisting essentially of the normal alpha olefin (s) "or variations thereof refers to the commercially available normal alpha olefin product (s). Commercially available normal alpha olefin products may, among other things, have non-nal alpha olefin impurities that have not been removed in the normal alpha olefin production process, such as vinylidene, internal olefins, branched alpha olefins, paraffins, and diolefins. One skilled in the art will recognize that the type and content of impurities present in the commercial n-alpha-olefin product varies depending on the commercial n-alpha-olefin product source. Also, when applied to a single carbon number of normal alpha olefins, the term "consisting essentially of " the nal alpha olefin (s)" refers to a material which differs from the stated nal alpha olefin carbon atoms which is not removed during the single carbon number normal alpha- (E. G., Less than 5, 4, 3, 2, or 1% by weight) of olefin having a carbon atom. As a result, the term " substantially consisting of normal alpha olefins "and variants thereof, unless explicitly stated otherwise, refers to the content / amount of non-linear alpha olefin components more strictly than the content / amount present in a particular commercial n- (With respect to the carbon number content of the non-mentioned carbon number). One source of commercially available alpha olefin products is those produced by ethylene oligomerization. The second source of commercially available alpha olefin products is those produced in the Fischer-Tropsch synthesis stream and those that are optionally separated. Commercially available normal alpha olefin product one source produced by ethylene oligomerization which may be used as olefin feedstock is Chevron Phillips Chemical Company LP, Woodland, Tex., USA. Other sources of commercially available normal alpha olefin products produced by ethylene oligomerization that can be used as olefin feedstock include, among others, Inneos Oligomers (Feluy, Belgium), Shell Chemicals Corporation (Houston, London), Idemitsu Kosan (Tokyo, Japan), and Mitsubishi Chemical Corporation (Tokyo, Japan). One source of commercially available normal alpha olefin products produced and optionally separated by the Fischer-Tropsch synthesis stream includes Sasol (Johannesburg, South Africa) above all.

"Aromatic group" means a general group formed by removing at least one hydrogen atom from an aromatic compound (as required and according to the specified group and at least one aromatic ring carbon atom). Thus, as used herein, the term "aromatic group" refers to an aromatic compound, ie, an annular conjugated hydrocarbon having (4n + 2) pi -electrons, where n is an integer from 1 to about 5, according to the Hueckel (4n + A branch refers to a group derived by removing one or more hydrogen atoms from a compound. The aromatic compound and thus the "aromatic group" may be monocyclic or polycyclic unless otherwise specified. The aromatic compounds are called "arenes" (hydrocarbon aromatics) and "heteroarenes", which are called "heterarenes" (a continuous pi-electromagnetic system in which one or more methine (-C═) carbon atoms are aromatic- Heteroaromatic compounds formally derived from arenes in which the trivalent or divalent heteroatom is replaced with a heteroatom such as to maintain the number of out-of-plane electrons corresponding to < RTI ID = 0.0 > Although arene compounds and heteroarene compounds are mutually exclusive members of aromatic groups, compounds having both arene groups and heteroarene groups are generally regarded as heteroarene compounds. Aromatic compounds, arenes, and heteroarenes may be mono- or polycyclic unless otherwise specified. Exemplary arenes include, but are not limited to, benzene, naphthalene, and toluene above all. Exemplary heteroarenes include, but are not limited to, furans, pyridines, and methylpyridines. When bonded to a transition metal, the aromatic group may be described according to the conventional eta ^x (etha-x) nomenclature, where x is coordinated to the transition metal or, for example, Lt; / RTI > The term "substituted ", as used herein, is used to describe an aromatic group in which a non-hydrogen moiety formally substitutes hydrogen in the group, and is non-limitingly intended.

An "aryl group" is a group derived by formally removing a hydrogen atom from an aromatic hydrocarbon ring carbon atom from an arene compound. An exemplary "aryl group" is ortho -tolyl ( o -tolyl), and the structure is as follows.

Similarly, "arylene group" means a group formed by removing two hydrogen atoms (from at least one aromatic hydrocarbon ring carbon) from arene.

"Argin group" means a general group formed by removing one or more hydrogen atoms from arene (according to the specified group, and as necessary, at least one aromatic hydrocarbon ring carbon). However, if it has both a gigaprene and a heteroarene moiety, then the grouping will depend on the particular moiety from which the hydrogen atom is removed, i.e., if the hydrogen is removed from the aromatic hydrocarbon ring or cyclic carbon atom, then the arene group and the hydrogen is a heteroaromatic ring or cyclic carbon If it is from an atom, it is a heteroarene group. When bonded to a transition metal, the "aryl group,""arylenegroup," and "arene group" may be described according to the conventional η ^x (eta-x) nomenclature wherein x is coordinated to the transition metal, For example, it is an integer corresponding to the number of atoms expected to coordinate according to the 18-electron rule

"Heterocyclic compounds" are cyclic compounds having at least two different atoms as ring atoms. For example, the heterocyclic compound may be selected from among carbon and nitrogen (such as tetrahydro pyrrole), carbon and oxygen (such as tetrahydrofuran), or carbon and sulfur (such as tetrahydrothiophene ). ≪ / RTI > The heterocyclic compound and the heterocyclic group may be aliphatic or aromatic. When bonded to a transition metal, the heterocyclic compound can be described according to the conventional eta ^x (etha-x) nomenclature, where x is coordinated to the transition metal or, for example, It is an integer that corresponds to the number of atoms.

 A "heterocyclyl group" is a heterocyclic ring of a heterocyclic compound or a monovalent group formed by removing a hydrogen atom from a cyclic carbon atom. By specifying that a hydrogen atom is removed from a heterocyclic ring or a cyclic carbon atom, a "heterocyclyl group" is distinguished from a "cycloheteryl group" in which a hydrogen atom is removed from a heterocyclic ring or a cyclic heteroatom. For example, the pyrrolidin-2-yl group described below is an exemplary "heterocyclyl group " and the pyrrolidin-1-yl group described below is an exemplary" cycloheteryl group ".

Pyrrolidin-2-ylpyrrolidin-1-yl

             The term "heterocyclyl group"               "Cycloheteryl group"

Similarly, "heterocyclylene" or, more simply, "heterocyclylene" is a group formed by removing two hydrogen atoms from a heterocyclic compound, at least one of which is a heterocyclic ring or a cyclic carbon Removed. Thus, in "heterocyclylene ", at least one hydrogen is removed from the heterocyclic ring or cyclic carbon atom and the other hydrogen atom is replaced by any other carbon atom, for example the same heterocyclic ring or ring system Carbon atoms, different heterocyclic rings or cyclic ring carbon atoms, or non-cyclic carbon atoms. "Heterocyclic group" means a general group formed by removing one or more hydrogen atoms from a heterocyclic compound (as required and according to the specified group, and at at least one heterocyclic ring carbon atom). The "heterocyclyl group,""heterocyclylenegroup," and "heterocyclic group", when bonded to a transition metal, can be described according to the conventional η ^x (etha-x) nomenclature, Is an integer corresponding to the number of atoms coordinated to the metal or coordinated according to, for example, the 18-electron rule.

The "cycloheteryl group" is a monocyclic group formed by removing a hydrogen atom from a heterocyclic ring or cyclic heteroatom of a heterocyclic compound, as mentioned. By specifying that a hydrogen atom is removed from a heterocyclic ring or a cyclic heteroatom that is not a ring carbon atom, a "cycloheteryl group" is distinguished from a "heterocyclyl group" in which a hydrogen atom is removed from a heterocyclic ring or a cyclic carbon atom . Similarly, a "cycloheterylene group" is a group formed by removing two hydrogen atoms from a heterocyclic compound, at least one of which is removed from the heterocyclic ring or cyclic heteroatom of the heterocyclic compound; Other hydrogen atoms may be removed from any other atoms, such as a heterocyclic ring or ring system ring carbon atom, another heterocyclic ring or ring system heteroatom, or a non-ring atom (carbon or heteroatom) . "Cyclohetero group" means a general group formed by removing one or more hydrogen atoms in a heterocyclic compound (according to the specified group, if necessary, and at least one in the heterocyclic ring or cyclic heteroatom). When coupled to a transition metal, "cycloheteryl group,""cycloheterylenegroup," and "cyclohetero group" can be described according to the conventional η ^x (eta-x) nomenclature, where x is the transition metal Or an integer corresponding to the number of coordinated atoms predicted, for example, according to the 18-electron rule.

The "heteroaryl group" belongs to the "heterocyclyl group" and is a monovalent group formed by removing a hydrogen atom from a heteroaromatic ring or ring carbon atom of a heteroarylene compound. By specifying that a hydrogen atom is removed from a ring carbon atom, a "heteroaryl group" is distinguished from an "arylheteryl group" in which a hydrogen atom is removed from a heteroaromatic ring or ring system heteroatom. For example, the following indol-2-yl groups are exemplary "heteroaryl groups", and the indol-1-yl groups below are exemplary "arylheteryl groups".

Indol-2-ylindol-1-yl

                The term "heteroaryl group"  "Arylheteryl group"

Similarly, "heteroarylene group" means a group formed by removing two hydrogen atoms from a heteroarylene compound, at least one of which is removed from the heteroarene ring or cyclic carbon atom. Thus, in the "heteroarylene group", at least one hydrogen is removed from the heteroarylene ring or cyclic carbon atom, and the other hydrogen atom is any other carbon atom, such as a heteroarylene ring or cyclic carbon atom, or Lt; RTI ID = 0.0 > non-heteroarylene < / RTI > ring or cyclic atom. "Heteroareylene group" means a general group formed in a heteroarylene compound (optionally according to the specified group and at least one heteroarylene ring or cyclic carbon atom) by removal of one or more hydrogen atoms. The "heteroaryl group,""heteroarylenegroup," and "heteroareylene group", when bonded to a transition metal, can be described according to the conventional η ^x (etha-x) nomenclature, where x is a transition metal Or an integer corresponding to the number of coordination atoms predicted, for example, according to the 18-electron rule.

The "arylheteryl group" belongs to the "cycloheteryl group" and is a monovalent group formed by removing a hydrogen atom from a heteroaromatic ring or cyclic heteroatom of a heteroaryl compound as described above. By specifying that a hydrogen atom is removed from a heteroaromatic ring or a heteroaromatic ring or cyclic heteroatom that is not a cyclic carbon atom, an "arylheteryl group" means a "heteroaryl group ", in which a hydrogen atom is removed from a heteroaromatic ring or ring- . Similarly, "arylheterylene group" means a group formed by the removal of two hydrogen atoms from a heteroaryl compound, at least one of which is removed from the heteroaromatic ring or cyclic heteroatom of the heteroaryl compound; Other hydrogen atoms may be derived from any other atom, for example, a heteroaromatic compound, from a heteroaromatic ring or ring system ring carbon atom, from another heteroaromatic ring or ring system heteroatom, or from a non-ring atom (carbon or heteroatom) Can be removed. "Arylheteroaryl" means a general group formed by the removal of one or more hydrogen atoms at a heteroatom of a heteroarylene compound (optionally according to the specified group and in at least one heteroaromatic ring or ring system). When bonded to a transition metal, "arylheteryl group,""arylheterylenegroup," and "arylhetero group" may be described according to the conventional η ^x (eta-x) nomenclature, where x is the transition metal Or an integer corresponding to the number of coordinated atoms predicted, for example, according to the 18-electron rule.

An "organoheteryl group" is a monovalent group having carbon, and thus organic, but having a free valence at a non-carbon atom. Thus, the organoheteryl and organyl groups are complementary and mutually exclusive. The organic heteroaryl group may be cyclic or acyclic, and / or may be aliphatic or aromatic and thus may be an aliphatic "cycloheteryl group" such as pyrrolidin-1-yl, an aromatic "arylheteryl group" Cycloalkyl, cycloalkyl, cycloalkyl, cycloalkyl, cycloalkyl, cycloalkyl, cycloalkyl, cycloalkyl, cycloalkyl and cycloalkyl. Similarly, an "organic heterorylene group" is a divalent group having carbon and at least one heteroatom, having two free valencies, and at least one being a heteroatom. An "organic heterocycle" is a general group having at least one free valence from carbon and at least one heteroatom (depending on the group, and optionally at least one heteroatom) from the heteroatom. When bonded to a transition metal, an "organic heterocyclic group,""organic heteroring group," or "organic heterocyclic group" may be described according to the conventional η ^x (eta-x) nomenclature, Or an integer corresponding to the number of coordinated atoms predicted, for example, according to the 18-electron rule.

 An "aralkyl group" is an aryl-substituted alkyl group having a free valency at a non-aromatic carbon atom, such as, for example, a benzyl group. Similarly, an "aralkylene group" is an aryl-substituted alkylene group having two free valences on a single non-aromatic carbon atom or a free valence on two non-aromatic carbon atoms and the "aralkane group" Is a generalized aryl-substituted alkane group having one or more free valencies in the aromatic carbon atom (s). "Heteroaralkyl group" is a non-heteroaromatic ring or heteroaryl-substituted alkyl group having a free valence at the ring carbon atom. Similarly, a "heteroaralkylene group" means a single non-heteroaromatic ring or a heteroaryl-substituted alkylene group having two free valencies at the ring carbon atom or two non-heteroaromatic rings or free valencies at the ring carbon atoms And "heteroaralkane group" is a generalized aryl-substituted alkane group having at least one free valence at a non-heteroaromatic ring or ring carbon atom (s).

 "Halide" has a conventional meaning. Exemplary halides include fluorides, chlorides, bromides, and iodides.

An "oxygen group " also referred to as an" oxygen-linking group "is a chemical moiety having at least one free valence in an oxygen atom. Exemplary "oxygen groups" include, but are not limited to, hydroxy (-OH), -OR, -OC (O) R, -OSiR ₃ , -OPR ₂ , -OAlR ₂ , -OSiR ₂ , -OGR ₃ , _{3, -OSO 2 R, -OSO 2} OR, -OBR 2, -OB (OR) 2, -OAlR 2, -OGaR 2, -OP (O) R 2, -OAs (O) R 2, -OAlR 2 , And the like, including substituted analogues thereof. In one aspect, each R may independently be a hydrocarbyl group; For example, each R may independently be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted cycloalkyl, substituted aryl, or substituted aralkyl. In an "oxygen group" having one or more free valencies, the other free valences may be at an atom (s) other than oxygen, for example carbon, depending on the chemical structure and bonding principle.

"Hwanggi, " also referred to as" sulfur-bonding group ", is also a chemical moiety having at least one free valence in the sulfur atom. The exemplary "Astragalus (s)" means, including, but not limited to, -SH, -SR, -SCN, -S (O) R, -SO 2 R, and others, and including their substituted analogues . In one aspect, each R may independently be a hydrocarbyl group; For example, each R may independently be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted cycloalkyl, substituted aryl, or substituted aralkyl. In the "sulfur group" having one or more free valences, the other free valences may be at an atom (s) other than sulfur, for example carbon, depending on the chemical structure and bonding principle.

A "nitrogen group", also referred to as a "nitrogen-linking group," is a chemical moiety having at least one free valence in a nitrogen atom. Exemplary "nitrogen groups" include, but are not limited to, an amine group (-NH ₂ ), an N-substituted amine group (-NRH), an N, N -disubstituted amine group (-NR ₂ ) NHNH _2), N ¹ - substituted hydrazine map group (-NRNH ^_2), N ₂ - substituted hydrazine map group ^{(-NHNRH), N 2, N} 2 - disubstituted hydrazine map group (-NHNR _2), a nitro group (-NO ₂ ), an azido group (-N ₃ ), an amidyl group (-NHC (O) R), an N-substituted amido group (-NRC ≪ / RTI > In one aspect, each R may independently be a hydrocarbyl group; For example, each R may independently be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted cycloalkyl, substituted aryl, or substituted aralkyl. In the "nitrogen group" having one or more free valencies, the other free valences may be on any atom (s), eg carbon, other than nitrogen in the group according to their chemical structure and bonding principle.

"Popular ", also referred to as a " phosphorus-bond group " is a chemical moiety having at least one free valence in the phosphorus atom. Exemplary "hot" include, but are not limited _{to, -PH 2, -PHR, -PR 2} , -P (O) R 2, -P (OR) 2, -P (O) (OR) 2, -P ( NR ₂ ) ₂ , -P (O) (NR ₂ ) ₂ , and the like, including substituted analogs thereof. In one embodiment, each R may independently be a hydrocarbyl group; For example, each R may independently be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted cycloalkyl, substituted aryl, or substituted aralkyl. In "popularity" with one or more free valences, the other free valences may be on any atom (s), e.g. carbon, other than phosphorus in the group according to chemical structure and bonding principle.

An "arsenic group" also referred to as an "arsenic-linking group" is a chemical moiety having a free valence at an arsenic atom. Exemplary "non-small" will end, -AsH contains _{2, -AsHR, -AsR 2, -As} (O) R 2, -As (OR) 2, -As (O) (OR) 2, and other such , Substituted analogues thereof. In one embodiment, each R may independently be a hydrocarbyl group; For example, each R may independently be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted cycloalkyl, substituted aryl, or substituted aralkyl. In the "non-atomic group" having one or more free valences, the other free valences can be on any atom (s) other than arsenic, such as carbon, in the groups according to their chemical structure and bonding principle.

A "silicon group " also referred to as a" silicon-bond group "is a generalized chemical moiety having at least one free valence in the silicon atom. A "silyl group" is a chemical moiety having at least one free valence in a silicon atom. Exemplary "silyl group" is, but not _{limited, -SiH 3, -SiH 2 R,} -SiHR 2, -SiR 3, -SiR 2 OR, -SiR (OR) 2, -Si (OR) 3 , and other such . In one aspect, each R may independently be a hydrocarbyl group; For example, each R may independently be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted cycloalkyl, substituted aryl, or substituted aralkyl. In a "silicon group" having one or more free valencies, the other free valencies may be at any atom (s) other than silicon in the group, for example carbon, depending on the chemical structure and bonding principle.

A "germanium group " also referred to as a" germanium-linker "is a generic chemical moiety having at least one free valence in a germanium atom. A "germanyl group" is a chemical moiety having at least one free valence in a germanium atom. Exemplary "germanate group" is, but not _{limited, -GeH 3, -GeH 2 R,} -GeHR 2, -GeR 3, -GeR 2 OR, -GeR (OR) 2, -Ge (OR) 3 , and other And the like. In one aspect, each R may independently be a hydrocarbyl group; For example, each R may independently be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted cycloalkyl, substituted aryl, or substituted aralkyl. In a "germanium group" having one or more free valences, the other free valences may be on any atom (s) other than germanium in the group, for example carbon, depending on the chemical structure and bonding principle.

A "tinctor ", also referred to as a" tin-linker ", is a generic chemical moiety having at least one free valence in a tin atom. A "stannyl group" is a chemical moiety having at least one free valence in an atom. Exemplary "stannyl groups" include, but are not limited to, -SnH ₃ , -SnH ₂ R, -SnHR ₂ , -SnR _3, and -Sn (OR) ₃ . In one aspect, each R may independently be a hydrocarbyl group; For example, each R may independently be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted cycloalkyl, substituted aryl, or substituted aralkyl. In a "tin group" having one or more free valences, the other free valences may be on any atom (s) other than tin in the group, for example carbon, depending on the chemical structure and bonding principle.

The term " lead ", also referred to as a "lead-bonding group ", is a chemical moiety having a free valence in the lead atom. Exemplary "delivery" include, but are not limited to, include _{-PbH 3, -PbH 2 R, -PbHR} 2, -PbR 3 and -Pb (OR) _3. In one aspect, each R may independently be a hydrocarbyl group; For example, each R may independently be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted cycloalkyl, substituted aryl, or substituted aralkyl. In the "delivery time" having one or more free valencies, the other free valencies may be on any atom (s) other than lead in the group, for example carbon, depending on the chemical structure and bonding principle.

A "boron group", also referred to as a "boron-bond group" is a generic chemical moiety having at least one free valence in the boron atom. A "boronyl group" is a chemical moiety having at least one free valence in a boron atom. Exemplary "borough group" include, but are not limited to, include _{-BH 2, -BHR, -BR 2,} -BR (OR), -B (OR) 2, and others. In one aspect, each R may independently be a hydrocarbyl group; For example, each R may independently be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted cycloalkyl, substituted aryl, or substituted aralkyl. In a "boron group" having one or more free valencies, the other free valencies may be at any atom (s) other than boron in the group, e.g. carbon, depending on the chemical structure and bonding principle.

"Aluminum group ", also referred to as" aluminum-bonding group ", is a generic chemical moiety having at least one free valence in the aluminum atom. An "aluminyl group" is a chemical moiety having at least one free valence in the aluminum atom. Exemplary "allyl groups" include, but are not limited to, -AlH ₂ , -AlHR, -AlR ₂ , -AlR (OR), -Al (OR) ₂ , and the like. In one aspect, each R may independently be a hydrocarbyl group; For example, each R may independently be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted cycloalkyl, substituted aryl, or substituted aralkyl. In an "aluminum group" having one or more free valences, the other free valencies can be on any atom (s) other than aluminum in the group, e.g. carbon, depending on the chemical structure and bonding principle.

Quot ;, " germanium group ", "germanium group," "Quot;, "borate group ", " borate group "," aluminum group ", and the like, these groups may include a generic "R" In each instance, R is independently an organyl group; Otherwise, a hydrocarbyl group; Otherwise, an alkyl group; Otherwise, an aliphatic group; Otherwise, a cycloalkyl group; Otherwise, an alkenyl group; Otherwise, an alkynyl group; Otherwise, an aromatic group; Otherwise, an aryl group; Otherwise, a heterocyclyl group; Otherwise, a cycloheteryl group; Otherwise, a heteroaryl group; Otherwise, an arylheteryl group; Otherwise, an organic heterocyclic group; Otherwise, an aralkyl group; Otherwise, heteroaralkyl groups; Alternatively, it can be a halide.

"Organoaluminum compound," is used to describe any compound having an aluminum-carbon bond. Thus, organoaluminum compounds include, but are not limited to, hydrocarbylaluminum compounds such as trihydrocarbyl-, dihydrocarbyl-, or monohydrocarbylaluminum compounds; Hydrocarbyl aluminum halides; Hydrocarbylalumoxane compounds; And aluminate compounds including aluminum-organyl bonds such as tetrakis ( p -tolyl) aluminate.

 "Identifiable crystallization" is determined by differential scanning calorimetry (DSC). "Identifiable crystallization" is determined according to ASTM D 3418, which proceeds with two heated scans that are intermittently cooled. Although referred to as crystallization, the term includes an identifiable melting determined by thermal analysis using a differential scanning calorimeter (DSC). Prior to each heating scan, the sample is cooled to -60 ° C and held at -60 ° C for 5 minutes. The first heating scan and the second heating scanning proceed from -60 占 폚 to 100 占 폚 at a heating rate of 10 占 폚 / min. The intermediate cooling scan proceeds from 100 占 폚 to -60 占 폚 at a rate of 10 占 폚 / min. The DSC is performed at a nitrogen flow rate of 20 cc / min (cubic centimeters per minute). The crystallization temperature (if present) or the melting temperature (if present), and the enthalpy of crystallization (if present) or the melting enthalpy (if present) are respectively taken as the temperature and enthalpy of the DSC crystallization transition or DSC melt transition of the secondary heat scan, Or fever.

"Solid superacid acid" or "SSA" is used as a synonym for a solid oxide chemically treated with an electron attracting anion, or a "chemically treated solid oxide ". SSA is a solid activator derived from a solid oxide chemically treated with an electron attracting anion as provided herein.

 The term " substantially optically pure "means a mixture of enantiomers with an enantiomeric excess of at least 99.5%.

The term referring to a "substantially absent" of a particular alpha olefin in different alpha olefin samples, for example, the description in which the alpha olefin monomer is derived from PAO in an alpha olefin sample that is "substantially free of 1-decene" Lt; RTI ID = 0.0 > of alpha olefin monomers. ≪ / RTI > For example, commercial samples of 1-octene and 1-dodecene can contain up to about 1% by weight of 1-decene, and when these 1-octene and 1-dodecene samples are characterized, Quot; does not include 1-decene "or" substantially 1-decene-free " Thus, the non-1-decene alpha olefin monomers used herein may include the amount of 1-decene present in commercially available alpha olefins.

The term " pre-contacting "as used herein means that the first mixture is" post-contact "of the catalytic components to be contacted during the second period or the first mixture of catalytic components to be contacted during the first period of time before being used to form the second mixture . ≪ / RTI > For example, a pre-contact mixture may be described as a mixture of a metallocene compound, an olefin monomer, and an organoaluminum compound before the mixture is contacted with the chemically treated solid oxide and optionally further organoaluminum compound. Thus, "pre-contact" describes components that are in contact with each other before contacting the additional components in the second, post-contact mixture. Thus, such a substrate may sometimes distinguish between the components used in the preparation of the pre-contact mixture and the components after preparation of the mixture. For example, according to this disclosure, there is provided a method of making a pre-contact organoaluminum compound, which is contacted with metallocenes and olefin monomers to form at least one different chemical compound, Aluminum compounds can be distinguished. In this case, the pre-contact organoaluminum compound or component may be described as comprising an organoaluminum compound used to prepare the pre-contact mixture.

Similarly, the term "post contact" is used herein to describe a second mixture of catalytic components that are contacted during a second period of time, one configuration of which includes a " 1 mixture. For example, the postcontact mixture describes a mixture of a first metallocene compound, a first metallocene compound, an olefin monomer, an organoaluminum compound, and a chemically treated solid oxide, Is formed by contact of any additional components added to make the contact mixture. In this example, the additional component added to prepare the postcontact mixture is a chemically treated solid oxide, and optionally an organoaluminum compound that is the same as or different from the organoaluminum compound used to make the pre-contact mixture as described herein . Thus, the components used in the preparation of the post-contact mixture according to the present disclosure and sometimes the components thereof after the mixture has been prepared can sometimes be distinguished.

As used herein, the term "metallocene" refers to a metal compound and at least one pi-bonded η ^{x ≥5} ligand; E.g. ^{≥5 x} η - hydrocarbyl, ^{ηx ≥5} - arene, η ^{x ≥5} - hetero arene, η ^{x ≥5} - heterocyclic, η ^{x ≥5} - Organic carbonyl, or ^{≥5 x} η - organic Heteroaryl or moiety conjugated with an aromatic (e.g.,? ⁵ -cycloalkadienyl-type) or (4n + 2) pi -electron, wherein n is an integer, usually 1 or 2 ⁵ -alkadienyl-type) organometallic coordination compound. In this embodiment, the IUPAC definition for the "metallocene" (IUPAC Chemical Dictionary, Second Edition (1997)) is more restrictive than the "metallocene" definition herein; The IUPAC definition for "metallocene" is therefore not used herein. In the present invention, such a ligand is referred to as Group I ligand, and a compound having at least one such ligand is referred to as metallocene. For example, the metallocene may comprise at least one pi-bonded η ^{x ≥5} ligand; For example, an η ⁵ -cycloalkadienyl-type or η ⁵ -alkadienyl-type ligand such as η ⁵ -cyclopentadienyl, η ⁵ -indene, η ⁵ -fluorenyl, η ⁵ -Alkadienyl-, eta ⁶ -borate benzene-ligand, and the like. Thus, the metallocenes are designated as having η ^{x ≥ 5} moieties according to the conventional η ^x ( ^etha- x) nomenclature, where x is coordinated to the transition metal or, for example, It is an integer that corresponds to the number of atoms.

The term "linker" is used to describe the overall chemical moiety linking two groups (e.g., Group I ligands and other intramolecular ligands, or other Group I ligands or Group II ligands). "Connector" includes "bridges "having" bridging atom (s) ". Crosslinking involves the smallest number of consecutive atoms (crosslinking atoms) necessary to traverse the link between linked ligands (e.g., Group I ligand and other ligands connected thereto). In general, linking groups and bridges may contain any atom; For example, crosslinking may include C, Si, Ge, Sn, or any combination thereof. The linking group may be saturated or the linking group may be unsaturated. For example, in the following metallocenes, "linking group" is the overall hydrocarbylene group C (CH ₃ ) CH ₂ CH ₂ CH = CH ₂ , and "bridging" or "bridging atom" is a single carbon atom. Thus, so-called "constrained geometry" metallocene catalysts are included in the metallocenes of the catalyst compositions of the present invention.

In some instances, a "cyclic group" is referenced. Unless otherwise specified, "cyclic group" includes aromatic and cyclic aliphatic groups including homocyclic and heterocyclic groups.

Alpha olefin oligomers, heavy oligomer products, and poly alpha olefins - structure and properties

 "Alpha olefin oligomer" or "oligomer product" are terms used to denote a collection of alpha olefin dimer, alpha olefin trimer, and heavy alpha olefin oligomer produced in the oligomerization reaction. By "heavy oligomer product" is meant a product in which some lower alpha olefin oligomers and / or monomers have been removed from the oligomer product in the oligomerization reactor effluent. For example, "heavy oligomer product" can refer to a separation-post aggregate of alpha olefin dimer, alpha olefin trimer, and heavy alpha olefin oligomer. "Polyalphaolefins" (PAOs) are terms used to describe hydrogenated (e.g., hydrogenated heavy olefinic products) or substantially saturated alpha olefinic oligomers. Thus, polyalphaolefins (PAOs) are mixtures of hydrogenated (or otherwise, substantially saturated) alpha olefinic oligomers having units derived from alpha olefinic monomers. The alpha olefin oligomers and poly alpha olefins (PAO) prepared by the present invention can have properties that can be selected over a range of numerical ranges. These properties can be achieved by applying the methods and catalyst systems described herein. The PAO properties produced by the present invention may also be characterized by the content (e.g.,% by weight) of the hydrogenated alpha olefin monomers, hydrogenated alpha olefin dimer, hydrogenated trimer, and / or hydrogenated heavy oligomer present in the PAO Olefin monomer, saturated alpha olefin dimer, saturated trimer, and / or saturated heavy oligomer content). Thus, when applied to alpha olefinic monomers, dimers, and heavy oligomers, the term "hydrogenation ", as used herein, refers to either hydrogenation of the resulting oligomer (oligomeric product or heavy oligomeric product) Is used to reflect the degree of hydrogenation.

In general, alpha olefin oligomers refer to a collection of alpha olefin oligomers, including dimer, trimer, and / or heavy olefin oligomers (including alpha olefin monomer units of 4 or more). The alpha olefin monomers used to produce dimer, trimer, and heavy olefin oligomers in the oligomerization reaction may be the same or different. The oligomerization reactor effluent may, among other things, comprise an alpha olefin oligomer product, a residual non-oligomerized alpha olefin monomer, a solvent, and / or catalyst system components. In one embodiment, the reactor effluent may be treated to provide an alpha olefin oligomer product and / or an alpha olefin oligomer product comprising some or all of the alpha olefin monomer used to form the alpha olefin oligomer. Depending on the reactor effluent treatment method, the alpha olefin oligomers may comprise residual alpha olefin monomers (typically less than 1% by weight - other contents are described herein and may be used without limitation). In this embodiment, the alpha olefin oligomer is selected from the group consisting of the alpha olefin monomer (s) used in oligomer formation, the alpha olefin monomer units content in the alpha olefin oligomer, the dimer content in the alpha olefin oligomer, the trimer content in the alpha olefin oligomer, The contents of heavy oligomers in alpha olefin oligomers can be described as Mw, Mn, 100 占 폚 kinematic viscosity, 40 占 폚 kinematic viscosity, viscosity index, pour point, flash point, ignition point, furnace volatile, head-to-tail addition error. These features of the alpha olefinic oligomer are described herein independently and the alpha olefinic oligomer is the alpha olefin monomer used in the oligomer formation described herein, the alpha olefin monomer units content in alpha olefin oligomers described herein, the alpha olefinic monomers The dimer content in the oligomer, the trimeric content in the alpha olefin oligomer described herein, the content of heavy oligomers in the alpha olefin oligomer described herein, the Mw described herein, the Mn described herein, the 100 DEG C kinematic viscosity described herein, To-tail addition errors described herein, the viscosity index described herein, the pour point described herein, the flash point described herein, the flash point described herein, the low volatility described herein, and the head-to-tail addition errors described herein. In general, these features may be applied to any fraction of the alpha olefinic oligomer described herein (e. G., A heavy oligomer product) in any combination and in a non-limiting manner. In some embodiments, the alpha olefin oligomer can be separated (e.g., by distillation) to produce a heavy oligomer product. Depending on the separation method employed, at least some of the alpha olefin monomers, dimers, and / or trimers may be removed by the separation process. Additionally, depending on the separation method applied, the fractionation process can not remove all alpha olefin monomers and the heavy oligomer product can contain alpha olefin monomers. In some embodiments, the residual alpha olefin monomer content of the separated alpha olefin oligomer may be specified by any number provided herein.

In a non-limiting example, the alpha olefin monomer and alpha olefin oligomer product aggregate (i.e., reactor effluent) exiting the reactor contain: a) less than 15 wt% alpha olefin monomer, b) less than 20 wt% dimer, and c ) Greater than 60% by weight of heavy oligomers. In another embodiment, the alpha olefin monomer and alpha olefin oligomer product aggregate (i.e. reactor effluent) exiting the reactor comprises: a) less than 12.5 wt% alpha olefin monomer, b) less than 15 wt% dimer, and c) More than 65% by weight of heavy oligomers may be included. In some non-limiting embodiments, the alpha olefin oligomer product may be produced from alpha olefin monomers substantially consisting of C ₈ normal alpha olefins. Other embodiments are apparent from the description of the present invention.

In a non-limiting embodiment, the oligomeric product comprises: a) less than 20% dimer, and b) greater than 70% by weight of heavy oligomer, i) a 100 ° C kinematic viscosity of at least 15 cSt, ii) Lt; / RTI > In a non-limiting embodiment, the oligomeric product is produced from an alpha olefin monomer substantially consisting of a C ₈ normal alpha olefin and comprises: a) less than 15% dimer, and b) greater than 75% wt. Heavy oligomer; i) a kinematic viscosity at 100 占 폚 of 30 cSt to 50 cSt; ii) a viscosity index of 150 to 260; In a non-limiting embodiment, the oligomer product is produced from an alpha olefin monomer substantially consisting of a C ₈ normal alpha olefin, and comprises: a) less than 12 wt% dimer; and b) greater than 75 wt% heavy oligomer; i) a kinematic viscosity at 100 占 폚 of 80 cSt to 140 cSt, and ii) a viscosity index of 150 to 260. Other embodiments are apparent from the description of the present invention.

In a non-limiting example, the oligomer product (e.g., heavy oligomer product, or any other) obtained by separating the reactor effluent comprises less than 1% by weight residual alpha olefin monomer; Otherwise, less than 0.8% by weight; Otherwise, less than 0.6% by weight; Otherwise, less than 0.5 wt% t; Otherwise, less than 0.4% by weight; Otherwise, less than 0.3% by weight; Otherwise, less than 0.2% by weight; Alternatively, less than 0.1% by weight.

In a non-limiting embodiment, the heavy oligomer product comprises a) less than 1% by weight of alpha olefin monomer, b) less than 3% by weight of dimer, and c) more than 80% by weight of heavy oligomer; i) the kinematic viscosity at 100 ° C is at least 15 cSt; and ii) the viscosity index exceeds 150. In some non-limiting embodiments, the heavy oligomer product is produced from an alpha olefin monomer substantially consisting of a C ₈ normal alpha olefin, and the alpha olefin oligomer product comprises: a) less than 0.5 wt% alpha olefin monomer, b) 1.5 wt % Dimer, and c) greater than 88 wt.% Heavy oligomer; i) 100 占 폚 kinematic viscosity is 30 cSt to 50 cSt, and ii) viscosity index is 150 to 260. In another non-limiting embodiment, the heavy oligomer product is produced from an alpha olefin monomer substantially consisting of a C ₈ normal alpha olefin, wherein the alpha olefin oligomer product comprises: a) less than 0.4% alpha olefin monomer, b) less than 1.5% Dimer, and c) greater than 88% by weight of heavy oligomers; i) a kinematic viscosity at 100 占 폚 of 80 cSt to 140 cSt, and ii) a viscosity index of 150 to 260. Other embodiments are apparent from the description of the present invention.

In another embodiment, PAO is selected from the group consisting of alpha olefin monomer (s) used in PAO formation, alpha olefin monomer units content in PAO, hydrogenated monomer content in PAO, hydrogenated dimer content in PAO, hydrogenated trimer content in PAO , The content of hydrogenated heavy oligomers in PAO, Mw, Mn, kinematic viscosity at 100 ° C, kinematic viscosity at 40 ° C, viscosity index, pour point, flash point, ignition point, furnace volatility, RPVOT results, head-to-tail addition error, Shear stability, polydispersity index, and / or identifiable crystallization, as determined by ASTM D6278-07. These PAO features are described herein independently and PAO is an alpha olefin monomer used in forming the PAO described herein, an alpha olefin monomer unit content in the PAO described herein, a hydrogenated monomer content in the PAO described herein, The hydrogenated dimer content in the PAOs described herein, the hydrogenated trimer content in the PAOs described herein, the hydrogenated heavy oligomer content in the PAOs described herein, the Mw described herein, the Mn described herein, the 100 DEG C kinematic viscosity described herein, The viscosity index described herein, the pour point described herein, the flash point described herein, the flash point described herein, the low volatility described herein, the RPVOT test results described herein, the head-to-tail addition errors described herein, the stereoregularity described herein , The Bernoulli Index described herein, and / or the identity of the identifiable crystallization described herein It can be described as a combination of righteousness.

For example, in a non-limiting example, polyalphaolefins (PAOs) derived from heavy-chain oligomer product hydrogenation have a Bernoulli index of less than 1.65; Alternatively, may be in the range of 1.1 +/- 0.4. In another non-limiting embodiment, the polyalphaolefins have no discernible crystallization above -40 DEG C as determined by differential scanning calorimetry in accordance with ASTM D 3418. The polyalphaolefin also has an RPVOT measured according to ASTM D2272 in the presence of 0.5% by weight of Naugalube (R) APAN antioxidant for at least 2,100 minutes with a pour point of -30 ° C to -90 ° C , Polyalphaolefins may have a Bernoulli index of less than 1.65 or in the range of 1.1 +/- 0.4, or any combination of these properties. Other embodiments are apparent from the description of the present invention.

In one embodiment, the alpha olefin oligomer, the alpha-olefin oligomer optional fraction, and / or the poly alpha olefin produced by the process described herein are alpha olefins; Alternatively, it may be produced using olefin monomers including normal alpha olefins. In an embodiment, the olefin monomer comprises at least 60%, 70%, 75%, 80%, 82.5%, 85%, 87.5%, 90%, 91%, 92% 94 wt%, 95 wt%, 96 wt%, 97 wt%, or 98 wt% alpha olefin. In some embodiments, the olefin monomer comprises at least 60 wt%, 70 wt%, 75 wt%, 80 wt%. 97, 94, 95, 95, 96, 97, or 98 weight percent of the total weight of the composition, 82.5 wt%, 85 wt%, 87.5 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt% Of normal alpha olefins. In general, the alpha olefins of the olefinic monomers may be any of the alpha olefins or normal alpha olefins described herein (single or blend).

A wide range of alpha olefin monomers can be oligomerized according to the methods provided herein. For example, the process described herein can be applied to alpha olefin monomers from propylene to waxes having 70 or 75 carbon atoms. In one embodiment and in any of the embodiments described herein, the alpha olefin oligomer, any fraction of the alpha olefin oligomer, and / or the PAO is a C ₃ to C ₇₀ alpha olefin; Alternatively, C ₃ to C ₄₀ alpha olefins; Alternatively, C ₄ to C ₂₀ alpha olefins; Alternatively, C ₅ to C ₁₈ alpha olefins; Alternatively, C ₆ to C ₁₆ alpha olefins; Or alternatively from alpha olefin monomers consisting essentially of, or consisting of C ₈ to C ₁₂ alpha olefins. In an embodiment, the alpha olefin oligomer, any fraction of the alpha olefinic oligomer, and / or the PAO is selected from the group consisting of C ₆ alpha olefins, C ₈ alpha olefins, C ₁₀ alpha olefins, C ₁₂ alpha olefins, C ₁₄ alpha olefins, C ₁₆ alpha olefins, Or any combination thereof; Alternatively, C ₈ alpha olefins, C ₁₀ alpha olefins, C ₁₂ alpha olefins, or any combination thereof; Otherwise, C ₆ alpha olefin; Otherwise, C ₈ alpha olefins; Otherwise, C ₁₀ alpha olefins; Alternatively, C ₁₂ alpha olefins; Otherwise, C ₁₄ alpha olefins; Otherwise, C ₁₆ alpha olefin; Or alternatively, from alpha olefin monomers comprising, or consisting essentially of, C ₁₈ alpha olefins. In other embodiments and in any suitable embodiment described herein, the alpha olefin oligomer, any fraction of the alpha olefin oligomer, and / or the PAO is a C ₃ to C ₇₀ normal alpha olefin; Alternatively, C ₃ to C ₄₀ normal alpha olefins; Alternatively, C ₄ to C ₂₀ normal alpha olefins; Alternatively, C ₅ to C ₁₈ normal alpha olefins; Alternatively, C ₆ to C ₁₆ normal alpha olefins; Or alternatively from alpha olefin monomers consisting essentially of, or consisting of C ₈ to C ₁₂ normal alpha olefins. In an embodiment, the alpha olefin oligomer, any fraction of the alpha olefin oligomer, and / or the PAO is selected from the group consisting of C ₆ normal alpha olefins, C ₈ normal alpha olefins, C ₁₀ normal alpha olefins, C ₁₂ normal alpha olefins, C ₁₄ normal alpha olefins, C ₁₆ normal alpha olefins, or any combination thereof; Alternatively, C ₈ normal alpha olefins, C ₁₀ normal alpha olefins, C ₁₂ normal alpha olefins, or any combination thereof; Otherwise, C ₆ normal alpha olefins; Otherwise, C ₆ normal alpha olefins; Alternatively, C ₈ normal alpha olefins; Alternatively, C ₁₀ normal alpha olefins; Alternatively, C ₁₂ normal alpha olefins; Alternatively, C ₁₄ normal alpha olefins; Otherwise, C ₁₆ normal alpha olefins; Or alternatively, from alpha olefin monomers consisting essentially of, or consisting of, C ₁₈ normal alpha olefins.

In one embodiment and in any of the embodiments described herein, the alpha olefin oligomer, any fraction of the alpha olefin oligomer, and / or the PAO is selected from the group consisting of 1-pentene, 1-hexene, 1-heptene, Undecene, 1-undecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, or any combination thereof; Alternatively, it is possible to use 1-pentene, 1-heptene, 1-octene, 1-nonene, Hexadiene, or any combination thereof; Alternatively, it may be produced from an alpha olefin monomer comprising or consisting essentially of 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, or any combination thereof. In some embodiments, the alpha olefin oligomer, any fraction of the alpha olefinic oligomer, and / or the PAO is selected from the group consisting of 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, Or any combination thereof; Alternatively, it may be produced from an alpha olefin monomer consisting essentially of or consisting of 1-octene, 1-decene, 1-dodecene, or any combination thereof. In another embodiment, the alpha olefin oligomer, any fraction of alpha olefinic oligomer, and / or PAO is selected from the group consisting of 1-pentene; Alternatively, 1-hexene; Alternatively, 1-heptene; Alternatively, 1-octene; Otherwise, 1-nonene; Otherwise, 1-decene; Otherwise, 1-undecene; Otherwise, 1-dodecene; Alternatively, 1-tridecene; Otherwise, 1-tetradecene; Alternatively, 1-pentadecene; Otherwise, 1-hexadecene; Alternatively, 1-heptadecene; Or alternatively from alpha olefin monomers consisting essentially of, or consisting of 1-octadecene.

In one embodiment and in any of the embodiments described herein, the alpha olefin oligomer, any fraction of the alpha olefin oligomer, and / or the PAO has the formula CH ₂ = CH (CH ₂ ) _n CH ₃ wherein n is from 1 to 17 essence; Alternatively, the formula _{CH 2 = CH (CH 2)} n CH 3, where n is an integer from 2 to 15; Alternatively, the formula _{CH 2 = CH (CH 2)} n CH 3, where n is an integer from 3 to 13; Alternatively, the formula _{CH 2 = CH (CH 2)} n CH 3, where n is an integer from 5 to 9; Or alternatively from alpha olefin monomers consisting essentially of, or consisting of alpha olefins having the formula CH ₂ = CH (CH ₂ ) _n CH ₃ . In some embodiments, the alpha olefin oligomer, any fraction of alpha olefinic oligomer, and / or PAO is an alpha olefin having the formula CH ₂ = CH (CH ₂ ) _n CH ₃ , wherein n is 3; Alternatively, an alpha olefin having the formula CH ₂ = CH (CH ₂ ) _n CH ₃ , wherein n is 5; Alternatively, an alpha olefin having the formula CH ₂ = CH (CH ₂ ) _n CH ₃ , wherein n is 7; Alternatively, an alpha olefin having the formula CH ₂ = CH (CH ₂ ) _n CH ₃ , wherein n is 9; Alternatively, an alpha olefin having the formula CH ₂ = CH (CH ₂ ) _n CH ₃ , wherein n is 11; Alternatively, an alpha olefin having the formula CH ₂ = CH (CH ₂ ) _n CH ₃ , wherein n is 13; Alternatively, n may be generated from alpha olefin monomers consisting essentially of, or consisting of alpha olefins having the formula CH ₂ = CH (CH ₂ ) _n CH ₃ ,

In one embodiment, the alpha olefin oligomer, any fraction of alpha olefin oligomer, and / or PAO produced according to the process described herein is a blend of alpha olefins; Or alternatively, olefin monomers comprising or consisting essentially of a blend of normal alpha olefins. Generally, olefin monomers are blends of any of the alpha olefins described herein; Or alternatively, any of the normal alpha olefins described herein. In an embodiment, the blend of alpha olefins comprises at least 50 wt%, at least 60 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 92.5 wt%, or 95 wt% Any alpha carbon number range of alpha olefins listed; Alternatively, any of the single carbon number alpha olefins described herein; Or alternatively, any single carbon number of normal alpha olefins described herein. In some non-limiting embodiments, the blend of normal alpha olefins comprises at least 50 wt%, at least 60 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 92.5 wt% 95% by weight of the normal alpha olefins in any carbon number range described herein; Alternatively, any combination of the single mono carbon number of the normal alpha olefins described herein; Or alternatively, any of the number of normal alpha olefins described herein.

In other embodiments, the alpha olefin oligomer, any fraction of the alpha olefin oligomer, and / or the PAO produced according to the process described herein may be produced using alpha olefin monomers comprising or consisting essentially of a blend of the normal alpha olefins have. Generally, the blend of alpha olefins may be a blend of any alpha olefins described herein. In an embodiment, the blend of alpha olefins comprises at least 50 wt%, at least 60 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 92.5 wt%, or 95 wt% Any alpha carbon number range of alpha olefins listed; Alternatively, any combination of alpha-olefins of the single carbon number described herein; Or alternatively, any of the number of alpha olefins described herein. In another embodiment, the alpha olefin oligomer, any fraction of the alpha olefin oligomer, and / or the PAO produced according to the process described herein are formed using a normal alpha olefin monomer consisting essentially of or consisting of a blend of the normal alpha olefins . Generally, the blend of the normal alpha-olefins may be a blend of any of the normal alpha-olefins described herein. In an embodiment, the blend of normal alpha olefins comprises at least 50 wt%, at least 60 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 92.5 wt%, or 95 wt% Normal alpha olefins in the range of any carbon number described in " Alternatively, any combination of any single carbon number of normal alpha olefins described herein; Or alternatively, any of the number of normal alpha olefins described herein.

In a non-limiting example, the olefinic monomer comprises at least 80% by weight of a C ₆ to C ₁₆ alpha olefin; Alternatively at least 60% by weight of C ₆ alpha-olefins and C ₁₄ alpha-olefins; Alternatively, at least 90% by weight of C ₈ to C ₁₂ normal alpha olefin; Alternatively, at least 85% by weight of 1-hexene, 1-decene, and 1-tetradecene; Alternatively at least 75% by weight of 1-octene; Or alternatively a blend of alpha olefins comprising a normal alpha olefin substantially consisting of at least 75% by weight of 1-octene. In some non-limiting embodiments, the single carbon number of alpha olefins that can be used in the alpha olefin blend is selected from the group consisting of C ₆ alpha olefins; Otherwise, C ₈ alpha olefins; Otherwise, C ₁₀ alpha olefins; Alternatively, C ₁₂ alpha olefins; Otherwise, C ₁₄ alpha olefins; Or alternatively may be substantially composed of C ₁₆ alpha olefins. In other non-limiting embodiments, the single carbon number of the normal alpha olefins that can be used in the alpha olefin blend or the normal alpha olefin blend is selected from the group consisting of C ₆ normal alpha olefins; Alternatively, C ₈ normal alpha olefins; Alternatively, C ₁₀ normal alpha olefins; Alternatively, C ₁₂ normal alpha olefins; Alternatively, C ₁₄ normal alpha olefins; Or alternatively may consist essentially of C ₁₆ normal alpha olefins. Other possible blends that can be used as olefinic monomers, alpha olefins, or n-alpha olefin monomers are apparent from this disclosure.

As noted, alpha olefin oligomers, any fractions of alpha olefin oligomers, and / or poly alpha olefins of any embodiment or example can be produced by alpha olefin oligomerization. The alpha olefin oligomers produced by oligomerization include units derived from alpha olefin monomers. It will be understood by those skilled in the art that the catalyst systems used to form alpha olefin oligomers can isomerize alpha olefin monomers to non-alpha olefins (e.g., internal olefins). Alternatively or additionally, the alpha olefin feedstock may have a non-alpha olefin content. Depending on the catalyst system used, non-alpha olefins may be included in alpha olefin oligomers (thus poly alpha olefins include alpha olefin monomer units and combinations of internal olefin monomer units). In some instances, the catalyst system may limit the degree of alpha olefin isomerization and / or limit the non-alpha olefin content included in the alpha olefin oligomer. As a result, one characteristic of the alpha olefinic oligomer, any fraction of the alpha olefinic oligomer, and / or the poly alpha olefin may be the percentage alpha olefin units in the alpha olefin oligomer, alpha olefin oligomer fraction and / or PAO. Thus, in any of the disclosed embodiments, the alpha olefin oligomer, any fraction of the alpha olefin oligomer, and / or the poly alpha olefin described herein comprises at least 70% alpha olefin monomer units; Alternatively at least 75% alpha olefin monomer units; Alternatively at least 80% alpha olefin monomer units; Alternatively at least 85% alpha olefin monomer units; Alternatively at least 90% alpha olefin monomer units; Alternatively at least 95% of the alpha olefin monomer units; Alternatively at least 98% of the alpha olefin monomer units; Or alternatively, at least 99% alpha olefin monomer units. In other embodiments, alpha alpha olefin oligomers, alpha alpha olefin oligomer fractions, and / or poly alpha olefins in accordance with certain embodiments may be substantially comprised of alpha olefin monomer units. In general, alpha olefins may be any of the alpha olefins described herein.

In one embodiment, the aggregate of alpha olefin monomer and alpha olefin oligomer product, alpha olefin product, or alpha olefin oligomer product fraction in the reactor effluent according to the present invention comprises less than 20 weight percent alpha olefin monomer; Alternatively, less than 17.5 wt% alpha olefin monomer; Alternatively less than 15% by weight alpha olefin monomer; Alternatively, less than 12.5 wt% alpha olefin monomer; Alternatively less than 10% by weight of alpha olefin monomers; Alternatively, less than 9 weight percent alpha olefin monomer; Alternatively less than 8% by weight of alpha olefin monomers; Alternatively, less than 7 weight percent alpha olefin monomer; Alternatively less than 6% by weight alpha olefin monomers; Alternatively less than 5% by weight of alpha olefin monomers; Alternatively less than 4% by weight of alpha olefin monomers; Alternatively less than 3% by weight of alpha olefin monomers; Alternatively less than 2% by weight of alpha olefin monomers; Alternatively, less than 1% by weight of alpha olefin monomers; Alternatively, less than 0.8 wt% alpha olefin monomer; Alternatively less than 0.6% by weight alpha olefin monomer; Alternatively less than 0.5% by weight alpha olefin monomer; Alternatively, less than 0.4% by weight alpha olefin monomer; Alternatively less than 0.3% by weight alpha olefin monomers; Alternatively, less than 0.2% by weight alpha olefin monomer; Or alternatively, less than 0.1% by weight of alpha olefin monomers. In some embodiments, the alpha olefin monomer content may be referred to as residual alpha olefin monomers (such as, among other things, a separated reactor effluent or a separate olefin oligomer) and any of the alpha olefin monomer values described herein may be utilized . In one embodiment, the fraction of alpha olefin monomer and alpha olefin oligomer product, alpha olefin product, or fraction of alpha olefin oligomer product according to the present invention comprises less than 20 weight percent dimer; Alternatively, less than 19% by weight dimer; Alternatively, less than 18 wt% dimer; Alternatively less than 17% by weight dimer; Alternatively, less than 16% dimer; Alternatively, less than 15% by weight dimer; Alternatively, less than 14% by weight dimer; Alternatively, less than 13 wt% dimer; Alternatively, less than 12 wt% dimer; Alternatively, less than 11% by weight dimer; Alternatively less than 10% by weight dimer; Alternatively, less than 9 wt% dimer; Alternatively less than 8% by weight dimer; Alternatively, less than 7 wt% dimer; Alternatively less than 6% by weight dimer; Alternatively, less than 5% by weight dimer; Alternatively, less than 4% by weight dimer; Dimer less than 3% by weight; Less than 2.5 wt% dimer; Alternatively less than 2% by weight dimer; Alternatively, less than 1.75 wt% dimer; Alternatively, less than 1.5 wt% dimer; Alternatively, less than 1.25 wt% dimer; Alternatively, less than 1% by weight dimer; Alternatively, less than 0.9 wt% dimer; Alternatively, less than 0.8 wt% dimer; Alternatively, less than 0.7 wt% dimer; Alternatively, less than 0.6 wt% dimer; Alternatively, less than 0.5 wt% dimer; Alternatively, less than 0.4 wt% dimer; Alternatively, less than 0.3% by weight of dimer. In another embodiment, the fraction of alpha olefin monomer and alpha olefin oligomer product, alpha olefin product, or fraction of alpha olefin oligomer product according to the present invention comprises less than 20 wt% trimer; Otherwise, less than 17.5 wt% trimer; Alternatively, less than 15% by weight trimer; Alternatively, less than 12.5 wt% trimer; Alternatively, less than 10% by weight of trimer; Less than 7.5 wt% trimer; Alternatively, less than 5 wt% trimer; Alternatively, less than 4 wt% trimer; Alternatively, less than 3% by weight trimer; 2 wt% trimer; Alternatively, less than 1.75 wt% trimer; Alternatively, less than 1.5% by weight trimer; Alternatively, less than 1.25 wt% trimer; Alternatively, less than 1% by weight of trimer; Alternatively, less than 0.9 wt% trimer; Alternatively, less than 0.8 wt% trimer; Alternatively, less than 0.7 wt% trimer; Alternatively, less than 0.6% by weight trimer; Alternatively, less than 0.5% by weight trimer; Alternatively, less than 0.4% by weight trimer; Otherwise, less than 0.3% by weight trimer; Alternatively, less than 0.2% by weight trimer; Alternatively, less than 0.1% by weight of trimers. In another embodiment, the fraction of alpha olefin monomer and alpha olefin oligomer product, alpha olefin product, or fraction of alpha olefin oligomer product according to the present invention comprises at least 50 wt% heavy oligomer; Alternatively, at least 55 wt% heavy oligomers; Alternatively at least 60 wt% heavy oligomers; Alternatively, at least 62.5 wt% heavy oligomers; Alternatively at least 65 wt% heavy oligomers; Alternatively at least 67.5 wt% heavy oligomers; Alternatively at least 70 wt% heavy oligomers; Alternatively, at least 72.5 wt% heavy oligomers; Alternatively at least 75 wt% heavy oligomers; Alternatively, at least 77.5 wt% heavy oligomers; Alternatively at least 80 wt% heavy oligomers; At least 82.5 wt% heavy oligomers; Alternatively at least 85 wt% heavy oligomers; Alternatively at least 86 wt% heavy oligomers; Alternatively at least 87 wt% heavy oligomers; Alternatively at least 88 wt% heavy oligomers; Alternatively at least 89 wt% heavy oligomers; Alternatively at least 90 wt% heavy oligomers; Alternatively at least 91 wt% heavy oligomers; Alternatively at least 92 wt% heavy oligomers; Alternatively at least 93 wt% heavy oligomers; Alternatively at least 94 wt% heavy oligomers; Or alternatively at least 95% by weight of the heavy oligomer. In addition, suitable combinations of these alpha-olefin oligomer weight percent features can be applied to describe alpha olefin oligomer fractions as provided herein. Generally, the alpha olefin monomer, dimer, trimer, and heavy oligomer weight percent of the alpha olefin monomer and alpha olefin oligomer product aggregates satisfy formula monomer + dimer + trimer + heavy oligomer = 100. Generally, the dimer, trimer, and heavy oligomer weight percent of the alpha olefin product or alpha olefin oligomer product fractions meet the formula dimer + trimer + heavy oligomer = 100. However, when it is necessary to clarify, the monomer (residual monomer) content is mentioned (for example, when referring to a reactor effluent that has been classified over other compositions) and in this case the alpha olefin monomer, dimer, trimer, The oligomer weight% satisfies formula monomer + dimer + trimer + heavy oligomer = 100.

In one embodiment, the heavy oligomer product comprises less than 1% by weight alpha olefin monomer; Alternatively, less than 0.8 wt% alpha olefin monomer; Alternatively less than 0.6% by weight alpha olefin monomer; Alternatively less than 0.5% by weight alpha olefin monomer; Alternatively, less than 0.4% by weight alpha olefin monomer; Alternatively less than 0.3% by weight alpha olefin monomers; Alternatively, less than 0.2% by weight alpha olefin monomer; Or alternatively less than 0.1% by weight of alpha olefin monomers. In some embodiments, the alpha olefin monomer content of the heavy oligomer product may utilize any alpha olefin monomer value referred to and described as the residual alpha olefin monomer. In another embodiment, the heavy oligomer product or heavy oligomer product fraction according to the present invention comprises less than 10% dimer; Alternatively, less than 9 wt% dimer; Alternatively less than 8% by weight dimer; Alternatively, less than 7 wt% dimer; Alternatively less than 6% by weight dimer; Alternatively, less than 5% by weight dimer; Alternatively, less than 4.5 wt% dimer; Alternatively, less than 4% by weight dimer; Alternatively, less than 3% by weight dimer; Alternatively, less than 2.5 wt% dimer; Alternatively less than 2% by weight dimer; Alternatively, less than 1.75 wt% dimer; Alternatively, less than 1.5 wt% dimer; Alternatively, less than 1.25 wt% dimer; Alternatively, less than 1% by weight dimer; Alternatively, less than 0.9 wt% dimer; Alternatively, less than 0.8 wt% dimer; Alternatively, less than 0.7 wt% dimer; Alternatively, less than 0.6 wt% dimer; Alternatively, less than 0.5 wt% dimer; Alternatively, less than 0.4 wt% dimer; Alternatively, less than 0.3 wt% dimer; Alternatively, less than 0.2 wt% dimer; Or alternatively, less than 0.1% by weight dimer. In another embodiment, the fractions of the heavy oligomer product or the heavy oligomer product comprise less than 20 wt% trimer; Otherwise, less than 17.5 wt% trimer; Alternatively, less than 15% by weight trimer; Alternatively, less than 12.5 wt% trimer; Alternatively, less than 10% by weight of trimer; Less than 7.5 wt% trimer; Alternatively, less than 5 wt% trimer; Alternatively, less than 4 wt% trimer; Alternatively, less than 3% by weight trimer; 2 wt% trimer; Alternatively, less than 1.75 wt% trimer; Alternatively, less than 1.5% by weight trimer; Alternatively, less than 1.25 wt% trimer; Alternatively, less than 1% by weight of trimer; Alternatively, less than 0.9 wt% trimer; Alternatively, less than 0.8 wt% trimer; Alternatively, less than 0.7 wt% trimer; Alternatively, less than 0.6% by weight trimer; Alternatively, less than 0.5% by weight trimer; Alternatively, less than 0.4% by weight trimer; Otherwise, less than 0.3% by weight trimer; Alternatively, less than 0.2% by weight trimer; Alternatively, less than 0.1% by weight of the trimer. In another embodiment, the heavy oligomer product or heavy oligomer product fraction comprises at least 80 wt% heavy oligomer; At least 82.5 wt% heavy oligomers; Alternatively at least 85 wt% heavy oligomers; Alternatively at least 86 wt% heavy oligomers; Alternatively at least 87 wt% heavy oligomers; Alternatively at least 88 wt% heavy oligomers; Alternatively at least 89 wt% heavy oligomers; Alternatively at least 90 wt% heavy oligomers; Alternatively at least 91 wt% heavy oligomers; Alternatively at least 92 wt% heavy oligomers; Alternatively at least 93 wt% heavy oligomers; Alternatively at least 94 wt% heavy oligomers; Alternatively, at least 95 wt% heavy oligomers. In addition, any suitable combination of such heavy oligomer weight percent features may be applied to describe the heavy oligomer fraction as provided herein. Generally, the alpha olefin monomer, dimer, trimer, and heavy oligomer weight percent of the heavy oligomer product satisfy formula monomer + dimer + trimer + heavy oligomer = 100. In some instances, when the heavy oligomer composition needs to be referred to as an oligomer, the weight percent of the dimer, trimer, and heavy oligomer of the heavy oligomer product satisfies the formula dimer + trimer + heavy oligomer = 100.

 In one aspect, the PAOs provided by the present invention comprise less than 1% by weight of hydrogenated alpha olefin monomers; Alternatively less than 0.8% by weight hydrogenated alpha olefin monomer; Alternatively, less than 0.6% by weight of hydrogenated alpha olefin monomers; Alternatively, less than 0.5% by weight hydrogenated alpha olefin monomer; Alternatively, less than 0.4% by weight hydrogenated alpha olefin monomer; Alternatively less than 0.3% by weight hydrogenated alpha olefin monomers; Alternatively less than 0.2% by weight hydrogenated alpha olefin monomer; Alternatively, less than 0.1% by weight hydrogenated alpha olefin monomers. In another embodiment, the PAO made by the present invention comprises less than 10 wt% hydrogenated dimer; Alternatively less than 9% by weight hydrogenated dimer; Alternatively, less than 8 wt% hydrogenated dimer; Alternatively, less than 7 wt% hydrogenated dimer; Alternatively less than 6% by weight hydrogenated dimer; Alternatively, less than 5 wt% hydrogenated dimer; Alternatively less than 4% by weight hydrogenated dimer; Otherwise, 4.5 hydrogenated dimer; Otherwise, 3.5 hydrogenated dimer; Alternatively, less than 3 wt% hydrogenated dimer; Less than 2.5 wt% hydrogenated dimer; Alternatively less than 2% by weight hydrogenated dimer; Alternatively, less than 1.75 wt% hydrogenated dimer; Alternatively, less than 1.5 wt% hydrogenated dimer; Alternatively, less than 1.25 wt% hydrogenated dimer; Alternatively less than 1% by weight hydrogenated dimer; Alternatively, less than 0.9 wt% hydrogenated dimer; Alternatively, less than 0.8 wt% hydrogenated dimer; Alternatively, less than 0.7 wt% hydrogenated dimer; Alternatively, less than 0.6 wt% hydrogenated dimer; Alternatively less than 0.5% by weight hydrogenated dimer; Alternatively, less than 0.4 wt% hydrogenated dimer; Alternatively, less than 0.3 wt% hydrogenated dimer; Alternatively, less than 0.2 wt% hydrogenated dimer; Alternatively, less than 0.1% by weight hydrogenated dimer. In another embodiment, the PAO according to the present invention comprises less than 20% by weight of hydrogenated trimer; Alternatively less than 17.5 wt% hydrogenated trimer; Alternatively less than 15% by weight hydrogenated trimer; Alternatively, less than 12.5 wt% hydrogenated trimer; Alternatively less than 10% by weight of hydrogenated trimer; Less than 7.5 wt% hydrogenated trimer; Alternatively less than 5% by weight of hydrogenated trimer; Alternatively less than 4% by weight of hydrogenated trimer; Alternatively less than 3% by weight of hydrogenated trimer; Less than 2 wt% hydrogenated trimer; Alternatively, less than 1.75 wt% hydrogenated trimer; Alternatively less than 1.5% by weight of hydrogenated trimer; Alternatively, less than 1.25 wt% hydrogenated trimer; Alternatively less than 1% by weight of hydrogenated trimer; Alternatively, less than 0.9 wt% hydrogenated trimer; Alternatively, less than 0.8 wt% hydrogenated trimer; Alternatively less than 0.7% by weight of hydrogenated trimer; Alternatively less than 0.6% by weight hydrogenated trimer; Alternatively less than 0.5% by weight hydrogenated trimer; Alternatively less than 0.4% by weight of hydrogenated trimer; Alternatively less than 0.3% by weight hydrogenated trimer; Alternatively, less than 0.2 wt% hydrogenated trimer; Alternatively, less than 0.1% by weight hydrogenated trimer. In another embodiment, the PAO according to the present invention comprises at least 80 wt% hydrogenated heavy oligomer; At least 82.5 wt% hydrogenated heavy oligomer; Alternatively at least 85 wt% hydrogenated heavy oligomer; Alternatively at least 86 wt% hydrogenated heavy oligomer; Alternatively at least 87 wt% hydrogenated heavy oligomer; Alternatively at least 88 wt% hydrogenated heavy oligomer; Alternatively at least 89 wt% hydrogenated heavy oligomer; Alternatively at least 90 wt% hydrogenated heavy oligomer; Alternatively at least 91 wt% hydrogenated heavy oligomer; Alternatively at least 92 wt% hydrogenated heavy oligomer; Alternatively at least 93 wt% hydrogenated heavy oligomer; Alternatively at least 94 wt% hydrogenated heavy oligomer; Or alternatively, at least 95 wt% hydrogenated heavy oligomers. In addition, any suitable combination of these features may be applied to describe the PAO described herein. Generally, the wt% of the hydrogenated alpha olefin monomer, hydrogenated dimer, hydrogenated trimer, and hydrogenated heavy oligomer of PAO satisfies formula monomer + dimer + trimer + heavy oligomer = 100. In some instances, when it is necessary to refer to PAO only as an oligomer, the wt% of the hydrogenated dimer, the hydrogenated trimer, and the hydrogenated heavy oligomer of the PAO satisfy the formula dimer + trimer + heavy oligomer = 100. Hydrogenated monomers, hydrogenated dimers, hydrogenated trimer, and hydrogenated heavy olefins, when referring to PAO, can be referred to as (saturated) monomers, saturated dimers, saturated trimer, and saturated heavy oligomers, Any number associated with the sieve, the hydrogenated trimer, and the hydrogenated heavy olefin may be applied to each of the saturated forms.

In one embodiment, the alpha olefin oligomer, fraction of alpha olefin oligomer, heavy oligomer product, and / or PAO provided by the present invention have a Mw of at least 400; Otherwise, at least 500; Otherwise, at least 600; Otherwise, at least 700; Otherwise, at least 800; Otherwise, at least 900; Otherwise, at least 1,000; Otherwise, at least 1,250; Otherwise, at least 1,500; Otherwise, at least 1,750; Otherwise, at least 2,000; Otherwise, at least 2,250; Otherwise, at least 2,500; Otherwise, at least 2,750; Otherwise, at least 3,000; Otherwise, at least 3,500; Otherwise, at least 4,000; Otherwise, at least 4,500; Otherwise, at least 5,000; Otherwise, at least 5,500; Otherwise, at least 6,000; Otherwise, at least 6,500; Otherwise, at least 7,000; Otherwise, at least 7,500; Otherwise, at least 8,000; Otherwise, at least 8,500; Otherwise, at least 9,000; Otherwise, at least 9,500; Otherwise, at least 10,000; Otherwise, at least 11,000; Otherwise, at least 12,000; Otherwise, at least 13,000; Otherwise, at least 14,000; Otherwise, at least 15,000; Otherwise, at least 16,000; Otherwise, at least 17,000; Otherwise, at least 18,000; Otherwise, at least 19,000; Otherwise, at least 20,000; Otherwise, at least 22,500; Otherwise, at least 25,000; Or otherwise, at least 30,000. Unless otherwise specified, the alpha olefin oligomer, alpha olefin oligomer fraction, and / or PAO of the present invention have an Mw upper limit of 60,000; Otherwise, 55,000; Otherwise, 50,000; Otherwise, 47,500; Otherwise, 45,000; Otherwise, 42,500; Otherwise, 40,000; Otherwise, 37,500; Otherwise, 35,000; Otherwise, 32,500; Otherwise, 30,000; Otherwise, 27,500; Otherwise, 25,000; Otherwise, 22,500; Otherwise, 20,000; ; Otherwise, 19,000; Otherwise, 18,000; Otherwise, 17,000; Otherwise, 16,000; Otherwise, 15,000; ; Otherwise, 14,000; Otherwise, 13,000; Otherwise, 12,000; Otherwise, 11,000; Otherwise, 10,000; Otherwise, 9,000; Otherwise, 8,500; Otherwise, 8,000; Otherwise, 7,500; Otherwise, 7,000; Otherwise, 6,500; Otherwise, 6,000; Otherwise, 5,500; Otherwise, 5,000; Otherwise, 4,500; Otherwise, 4,000; Otherwise, 3,000; Otherwise, 2,750; Otherwise, 2,500; Otherwise, 2,000; Otherwise, 1,750; Otherwise, 1,500; Otherwise, 1,250; Otherwise, it is 1,000. In one embodiment, the alpha olefin oligomer, fraction of alpha olefin oligomer, heavy oligomer product, and / or PAO of the present invention can range in Mw from any lower PAO Mw described herein to any maximum PAO Mw described herein. In a non-limiting example, the alpha olefin oligomer, alpha olefin oligomer fraction, heavy oligomer product, and / or PAO of the present invention have Mw ranges from 1,500 to 15,000; Otherwise, 2,000 to 12,500; Alternatively, from 2,500 to 10,000. In some non-limiting embodiments, the PAO of the present invention has a Mw range of 2,000 to 4,500; Otherwise, 2,500 to 4,000; Alternatively, from 2,750 to 3,750. In other non-limiting embodiments, the PAO of the present invention has a Mw range of 3,500 to 6,000; Otherwise, 4,000 to 5,500; Alternatively, it may be from 4,250 to 5,250.

In one aspect, the alpha olefin oligomer, fraction of alpha olefin oligomer, heavy oligomer product, and / or PAO provided by the present invention has Mn of at least 400; Otherwise, at least 500; Otherwise, at least 600; Otherwise, at least 700; Otherwise, at least 800; Otherwise, at least 900; Otherwise, at least 1,000; Otherwise, at least 1,250; Otherwise, at least 1,500; Otherwise, at least 1,750; Otherwise, at least 2,000; Otherwise, at least 2,250; Otherwise, at least 2,500; Otherwise, at least 2,750; Otherwise, at least 3,000; Otherwise, at least 3,500; Otherwise, at least 4,000; Otherwise, at least 4,500; Otherwise, at least 5,000; Otherwise, at least 5,500; Otherwise, at least 6,000; Otherwise, at least 6,500; Otherwise, at least 7,000; Otherwise, at least 7,500; Otherwise, at least 8,000; Otherwise, at least 8,500; Otherwise, at least 9,000; Otherwise, at least 9,500; Otherwise, at least 10,000; Otherwise, at least 11,000; Otherwise, at least 12,000; Otherwise, at least 13,000; Otherwise, at least 14,000; Otherwise, at least 15,000; Otherwise, at least 16,000; Otherwise, at least 17,000; Otherwise, at least 18,000; Otherwise, at least 19,000; Otherwise, at least 20,000; Otherwise, at least 22,500; Otherwise, at least 25,000; Or otherwise, at least 30,000. Unless otherwise specified, the alpha olefin oligomer, alpha olefin oligomer fraction, and / or PAO of the present invention have an Mn upper limit of 60,000; Otherwise, 55,000; Otherwise, 50,000; Otherwise, 47,500; Otherwise, 45,000; Otherwise, 42,500; Otherwise, 40,000; Otherwise, 37,500; Otherwise, 35,000; Otherwise, 32,500; Otherwise, 30,000; Otherwise, 27,500; Otherwise, 25,000; Otherwise, 22,500; Otherwise, 20,000; ; Otherwise, 19,000; Otherwise, 18,000; Otherwise, 17,000; Otherwise, 16,000; Otherwise, 15,000; ; Otherwise, 14,000; Otherwise, 13,000; Otherwise, 12,000; Otherwise, 11,000; Otherwise, 10,000; Otherwise, 9,000; Otherwise, 8,500; Otherwise, 8,000; Otherwise, 7,500; Otherwise, 7,000; Otherwise, 6,500; Otherwise, 6,000; Otherwise, 5,500; Otherwise, 5,000; Otherwise, 4,500; Otherwise, 4,000; Otherwise, 3,000; Otherwise, 2,750; Otherwise, 2,500; Otherwise, 2,000; Otherwise, 1,750; Otherwise, 1,500; Otherwise, 1,250; Otherwise, it could be 1,000. In one embodiment, the alpha olefin oligomer, fraction of alpha olefin oligomer, heavy oligomer product, and / or PAO of the present invention may have any of the lower PAO Mn described herein, or any of the maximum PAO Mws described herein, in the Mw range. In a non-limiting example, the alpha olefin oligomer, alpha olefin oligomer fraction, heavy oligomer product, and / or PAO of the present invention have Mw ranges from 1,500 to 15,000; Otherwise, 2,000 to 12,500; Alternatively, from 2,500 to 10,000. In some non-limiting embodiments, the PAOs of the present invention have Mn ranges from 2,000 to 4,500; Otherwise, 2,500 to 4,000; Alternatively, from 2,750 to 3,750. In other non-limiting embodiments, the PAO of the present invention has a Mn range of 3,500 to 6,000; Otherwise, 4,000 to 5,500; Alternatively, it may be from 4,250 to 5,250.

The alpha olefin oligomer, alpha olefin oligomer fraction, heavy oligomer product, and / or PAO produced by the process described herein have a broad 100 ° C kinematic viscosity and / or a 40 ° C kinematic viscosity. For example, a material having a kinematic viscosity at 100 DEG C of at least 1,000 cSt is possible by the catalyst system and / or method provided herein. In one aspect of the present invention, the alpha olefin oligomer, the fraction of the alpha olefin oligomer, the heavy oligomer product, and / or the PAO has a kinematic viscosity at 100 DEG C of at least 15 cSt; Otherwise, at least 20 cSt; Otherwise, at least 25 cSt; Otherwise, at least 35 cSt; Otherwise, at least 45 cSt; Otherwise, at least 55 cSt; Otherwise, at least 65 cSt; Otherwise, at least 75 cSt; Otherwise, at least 85 cSt; Otherwise, at least 95 cSt; Otherwise, at least 105 cSt; Otherwise, at least 115 cSt; Otherwise, at least 125 cSt; Otherwise, at least 135 cSt; Otherwise, at least 145 cSt; Otherwise, at least 155 cSt; Otherwise, at least 165 cSt; Otherwise; Otherwise, at least 175 cSt; Otherwise, at least 200 cSt; Otherwise, unlike, at least 225 cSt; Otherwise, at least 250 cSt; Otherwise, at least 270 cSt; Otherwise, at least 300 cSt; Otherwise, at least 350 cSt; Otherwise, at least 400 cSt; Otherwise, at least 500 cSt; Otherwise, at least 600 cSt; Otherwise, at least 700 cSt; Otherwise, at least 800 cSt; Otherwise, at least 900 cSt; Otherwise, at least 1000 cSt; Otherwise, at least 1100 cSt; Or otherwise at least 1200 cSt. In one aspect of the present invention, the alpha olefin oligomer, fraction of alpha olefin oligomer, heavy oligomer product, and / or PAO have a 40 < 0 > C kinematic viscosity of at least 120 cSt; Otherwise, at least 130 cSt; Otherwise, at least 140 cSt; Otherwise, at least 150 cSt; Otherwise, at least 160 cSt; Otherwise, at least 170 cSt; Otherwise, at least 180 cSt; Otherwise, at least 190 cSt; Otherwise, at least 200 cSt; Otherwise, at least 225 cSt; Otherwise, at least 250 cSt; Otherwise, at least 270 cSt; Otherwise, at least 300 cSt; Otherwise, at least 350 cSt; Otherwise, at least 400 cSt; Otherwise, at least 500 cSt; Otherwise, at least 600 cSt; Otherwise, at least 700 cSt; Otherwise, at least 800 cSt; Otherwise, at least 900 cSt; Otherwise, at least 1000 cSt; Otherwise, at least 1100 cSt; Otherwise, at least 1200 cSt; Otherwise, at least 1300 cSt; Otherwise, at least 1400 cSt; Otherwise, at least 1500 cSt; Otherwise, at least 1600 cSt; Otherwise, at least 1700 cSt; Otherwise, at least 1800 cSt; Otherwise, at least 1900 cSt; Or otherwise at least 2000 cSt. In some embodiments, the alpha olefin oligomer, fraction of alpha olefin oligomer, heavy oligomer product, and / or PAO has a kinematic viscosity at 100 DEG C of from 15 to 1,500, alternatively from 15 to 1,250; Otherwise, from 15 to 1,000; Otherwise, from 15 to 750; Otherwise, 15 to 500; Alternatively 15 cSt to 250 cSt; Alternatively 20 cSt to 225 cSt; Otherwise, 25 cSt to 55 cSt; Alternatively 30 cSt to 50 cSt; Alternatively 32 cSt to 48 cSt; Otherwise, 35 cSt to 45 cSt; Alternatively 40 cSt to 80 cSt; Otherwise, 45 cSt to 75 cSt; Alternatively 50 cSt to 70 cSt; Alternatively 60 cSt to 100 cSt; Alternatively 65 cSt to 95 cSt; Alternatively 70 cSt to 90 cSt; Alternatively 80 cSt to 140 cSt; Alternatively 80 cSt to 120 cSt; Alternatively from 85 cSt to 115 cSt; Alternatively 90 cSt to 110 cSt; Alternatively 100 cSt to 140 cSt; Otherwise, from 105 cSt to 135 cSt; Alternatively 110 cSt to 130 cSt; Alternatively from 120 cSt to 180 cSt; Alternatively 130 cSt to 170 cSt; Alternatively 140 cSt to 160 cSt; Alternatively 150 cSt to 210 cSt; Alternatively 160 cSt to 200 cSt; Alternatively 150 cSt to 190 cSt; Alternatively 180 cSt to 240 cSt; Otherwise, 190 cSt to 230 cSt; Alternatively 200 cSt to 220 cSt; Alternatively 200 cSt to 300 cSt; Alternatively 220 cSt to 280 cSt; Otherwise, 235 to 265; Alternatively from 250 cSt to 350 cSt; Otherwise, 270 cSt to 330 cSt; Otherwise, 285 cSt to 315 cSt; Alternatively from 300 cSt to 400 cSt; Otherwise, 320 cSt to 380 cSt; Otherwise, 335 cSt to 365 cSt; Alternatively from 350 cSt to 450 cSt; Otherwise, 370 cSt to 430 cSt; Otherwise, 385 cSt to 415 cSt; Alternatively 400 cSt to 500 cSt; Otherwise, 420 cSt to 480 cSt; Otherwise, 435 cSt to 465 cSt; Otherwise, from 450 cSt to 550 cSt; Otherwise, 470 cSt to 530 cSt; Otherwise, 485 cSt to 515 cSt; Otherwise, 500 cSt to 700 cSt; Otherwise, 540 cSt to 660 cSt; Otherwise, 570 cSt to 630 cSt; Otherwise, 600 cSt to 800 cSt; Alternatively 640 cSt to 760 cSt; Otherwise, 670 cSt to 740 cSt; Otherwise, 700 cSt to 900 cSt; Otherwise, 740 cSt to 860 cSt; Otherwise, 770 cSt to 830 cSt; Otherwise, 800 cSt to 1,000 cSt; Otherwise, 840 cSt to 960 cSt; Otherwise, 870 cSt to 940 cSt; Otherwise, 900 cSt to 1,100 cSt; Otherwise, 940 cSt to 1,060 cSt; Alternatively from 970 cSt to 1,030 cSt. In some embodiments, the alpha olefin oligomer, fraction of alpha olefin oligomer, heavy oligomer product, and / or PAO has a 40 DEG C kinematic viscosity of 120 cSt to 2000 cSt. Alternatively, and in any of the embodiments described herein, the polyalphaolefins produced by the present invention have a 40 DEG C kinematic viscosity ranging from 150 cSt to 1750 cSt; Alternatively from 200 cSt to 1500 cSt.

The alpha olefin oligomer, fraction of alpha olefin oligomer, heavy oligomer product, and / or PAO provided by another aspect of the present invention has a viscosity index greater than 150; Otherwise, exceeded 155; Otherwise, greater than 160; Otherwise, exceeding 165; Otherwise, greater than 170; Otherwise, greater than 175; Otherwise, exceed 180; Otherwise, exceed 185; Otherwise, exceed 190; Or otherwise, exceeds 200. In another aspect of the invention, the alpha olefin oligomer, fraction of alpha olefin oligomer, heavy oligomer product, and / or PAO has a viscosity index of from 150 to 260; Otherwise, 155 to 245; Otherwise, 160 to 230; Or alternatively, from 165 to 220.

According to another embodiment, the alpha olefin oligomer, fraction of alpha olefin oligomer, heavy oligomer product, and / or PAO provided by the present invention has a pour point of less than 0 DEG C; Otherwise, less than -10 캜; Otherwise, less than -20 ° C; Otherwise, less than -30 ° C; Otherwise, less than -35 캜; Otherwise, less than -40 ° C; Otherwise, less than -45 캜; Otherwise, less than -50 ° C; Alternatively, may be less than -55 占 폚. Further, the alpha olefin oligomer, the fraction of the alpha olefin oligomer, the heavy oligomer product, and / or the PAO according to the present invention has a pour point of from 0 DEG C to -100 DEG C; Otherwise, between -10 ° C and -95 ° C; Alternatively -20 캜 to -90 캜; Otherwise, -30 캜 to -90 캜; Otherwise, from -35 ° C to -90 ° C; Alternatively -40 ° C to -90 ° C; Otherwise, -45 캜 to -90 캜; Alternatively -50 ° C to -85 ° C; Alternatively, from -55 占 폚 to -80 占 폚.

In an embodiment, the alpha olefin oligomer, the fraction of alpha olefin oligomer, the heavy oligomer product, and / or the PAO provided by the present invention have a flash point above 200 DEG C; Otherwise, greater than 225 ° C; Otherwise, above 250 ° C; Alternatively, may exceed 275 ° C. In some embodiments, the alpha olefin oligomer, fraction of alpha olefin oligomer, heavy oligomer product, and / or PAO provided by the present invention have an ignition point above 200 DEG C; Otherwise, greater than 225 ° C; Otherwise, above 250 ° C; Alternatively, may exceed 275 ° C. In another embodiment, the alpha olefin oligomer, the fraction of alpha olefin oligomer, the heavy oligomer product, and / or the PAO has less than 8% by weight volatile volatility; Otherwise, less than 8% by weight; Otherwise, less than 7% by weight; Otherwise, less than 6% by weight; Otherwise, less than 5% by weight; Otherwise, less than 4.5% by weight; Otherwise, less than 4% by weight; Otherwise, less than 3.5% by weight; Alternatively, less than 3% by weight; Otherwise, less than 2.5% by weight; Otherwise, less than 2% by weight; Otherwise, less than 1.5% by weight; Alternatively, less than 1% by weight.

In one embodiment, the oligomerization process described herein is primarily a stereoregular head-to-tail reaction in which alpha olefin monomers are reacted to produce alpha olefin oligomers. In some embodiments, the alpha olefin oligomer, any fraction of the alpha olefin oligomer (e.g., the heavy oligomer product), and / or the PAO comprises, or alternatively consists essentially of, the head-to-tail oligomer. In certain embodiments or disclosed embodiments, the alpha olefin oligomer, any fraction of the alpha olefin oligomer, the heavy oligomer product, and / or the PAO comprises a head-to-tail oligomer wherein less than 100 errors per 1000 alpha olefin monomers; Otherwise, less than 80 errors per 1000 alpha olefin monomer; Otherwise, less than 60 errors per 1000 alpha olefin monomer; Alternatively, there are less than 40 errors per 1000 alpha olefin monomer. In general, the number of errors (non-head-to-tail addition) is determined by relative ¹ H NMR or ¹³ C NMR peak intensities.

The polyalphaolefins described herein may have advantageous properties with respect to their oxidative stability. The test for oxidation stability is an RPVOT experiment measured according to ASTM D2272. In one embodiment, the polyalphaolefin has a melt index of at least 2,000 minutes; Otherwise, 2,100 minutes; Otherwise, 2,150 minutes; Otherwise, 2,200 minutes; Otherwise, 2,250 minutes; Otherwise, 2,300 minutes; Otherwise, 2,400 minutes; Otherwise, 2,500 minutes; Otherwise, 2,750 minutes; Or alternatively RPVOT as measured by ASTM D2272 in the presence of 0.5 weight percent Naugalube 占 APAN antioxidant at 3,000 minutes.

In other embodiments and in any of the embodiments described herein, the polyalphaolefins provided by the present invention are selected from the group consisting of mr (heterogeneous) triads, mm (homogeneous array) triplets, and / or rr (Alternating arrangement) triplet percentages. In one embodiment, the PAO has an mr (heterogeneous) triplicate percentage of 20% to 70%; Otherwise, 25% to 65%; Otherwise, 30% to 60%; Otherwise, 35% to 55%; Alternatively, from 40% to 50%. In another embodiment, the PAO is from 10% to 55% in mm (homologous sequence) triplicate percent; Otherwise, 15% to 50%; Otherwise, 20% to 45%; Or alternatively, from 25% to 45%. In another embodiment, the PAO is such that the mm (homologous) triplicate percentages are between 25% and 60%, relative to ¹ H NMR or ¹³ C NMR peak intensities; Otherwise, 30% to 55%; Otherwise, 32% to 50%; Otherwise, 35% to 48%; Alternatively, from 38% to 45%. In another embodiment, the PAO has an rr (alternating arrangement) triplicate percentage of 5% to 40%; Otherwise, 7.5% to 35%; Otherwise, 10% to 30%; Alternatively, from 12.5% to 25%. In another embodiment, the PAO is such that the rr (alternating sequence) triplicate percentages are between 2% and 35%, relative to ¹ H NMR or ¹³ C NMR peak intensities; Otherwise, 5% to 30%; Otherwise, 8% to 25%; Otherwise, 10% to 20%; Or alternatively, from 12% to 18%. In general, the triplet percentages satisfy the formula mm triplet + mr triplet + rr triplet = 100. Generally, the mm triplet, mr triplet, and rr triplet percentages are described by Il Kim, Jia-Min Zhou and Hoeil Chung, "Higher α-Olefin Polymerization by Zr Complex", J. of Polymer Science: Vol. As described in 38, 1687-1697 (2000) it can be determined using ¹ H NMR or ¹³ C NMR peak intensity.

A useful measure of the oligomer stereoregularity is the Bernoulli index B, which is defined as B = 4 [ mm ] [ rr ] / [ mr ] ² where [ mm ], [ rr ], and [ mr ] Allogeneic triplet, alternating triplet, and heterologous triplet. In this embodiment and in any of the embodiments described herein, the inventive PAO has a Bernoulli Index of less than 3; Otherwise, less than 2.5; Otherwise, less than 2; Otherwise, less than 1.75; Otherwise, less than 1.7; Otherwise, less than 1.65; Otherwise, less than 1.6; Otherwise, less than 1.55; Otherwise, less than 1.5; Otherwise, less than 1.45; Otherwise, less than 1.4; Otherwise, less than 1.35; Otherwise, less than 1.3; Otherwise, less than 1.25; Otherwise, less than 1.25; Alternatively, less than 1.15. According to another aspect, the polyalphaolefins provided by the present invention have a Bernoulli index range of 1.4 +/- 0.25; Otherwise, 1.4 ± 0.2; Otherwise, 1.4 ± 0.15; Otherwise, 1.4 ± 0.10; Otherwise, 1.3 ± 0.3; Otherwise, 1.3 ± 0.25; Otherwise, 1.3 ± 0.2; Otherwise, 1.3 ± 0.15; Otherwise, 1.4 ± 0.1; Otherwise, 1.2 ± 0.35; Otherwise, 1.2 ± 0.3; Otherwise, 1.2 ± 0.25; Otherwise, 1.2 ± 0.2; Otherwise, 1.2 ± 0.15; Otherwise, 1.1 ± 0.40; Otherwise, 1.1 ± 0.3; Otherwise, 1.1 ± 0.2; Otherwise, it is 1.1 + - 0.15. In addition, any combination of the features described herein can be provided in the PAOs produced by the methods described herein. In addition, the polyalphaolefins disclosed in certain embodiments may have shear stability as a viscosity drop of less than 1%, as determined in accordance with ASTM D6278-07. Otherwise, the polyalphaolefins produced by the present invention have a pore size of less than 0.75%; Otherwise, less than 0.5; Or otherwise have a shear stability as a viscosity drop of less than 0.25.

In another aspect, the polyalphaolefins disclosed in certain embodiments herein have a polydispersion index (PDI) of 1.4 to 3, as determined from Mn and Mw obtained by gel permeation chromatography. Alternatively, the polydispersity index (PDI) of the polyalphaolefins produced by the present invention is from 1.5 to 2.8; Otherwise, 1.6 to 2.6; Otherwise, 1.7 to 2.5; Otherwise, 1.8 to 2.3; Alternatively, from 1.9 to 2.1.

In another embodiment, the PAO may have features characterized by discernible crystallization. Generally, "identifiable crystallization" is determined by thermal analysis using differential scanning calorimetry (DSC) as described herein. In yet another embodiment, the PAO may have a crystallization-free characteristic that is discernible at -40 캜 or higher as determined by scanning calorimetry according to ASTM D 3418.

As described herein, PAO can be selected from the group consisting of alpha olefin monomers used in PAO formation, alpha olefin monomer units content in PAO, hydrogenated monomer content in PAO, hydrogenated dimer content in PAO, hydrogenated trimer content in PAO, Head-to-tail addition error, stereoregularity, Bernoulli index, according to ASTM D6278-07, hydrogenated heavy oligomer content in PAO, Mw, Mn, 100 캜 kinematic viscosity, 40 캜 kinematic viscosity, viscosity index, pour point, RPVOT Shear stability measured, polydispersity index, and / or any combination of identifiable crystallization. In a non-limiting embodiment, the present invention provides PAOs produced from alpha olefin monomers including C ₄ to C ₂₀ normal alpha olefins, wherein the PAOs comprise: a) less than 1% by weight hydrogenated alpha olefin monomer; b) % Hydrogenated dimer, and c) greater than 80 wt.% Hydrogenated heavy oligomer; i) the kinematic viscosity at 100 占 폚 is at least 15 cSt, ii) the viscosity index exceeds 150, and iii) the pour point is below 0 占 폚. Other embodiments of the PAO can be distinguished by this disclosure.

In another non-limiting embodiment, the present invention provides a PAO produced from alpha olefin monomers substantially consisting of C ₈ normal alpha olefins, wherein the PAO comprises: a) less than 0.4% by weight hydrogenated alpha olefin monomer, b) less than 1.5% Of hydrogenated dimer, and c) greater than 88 wt% of hydrogenated heavy oligomer; i) 100 占 폚 kinematic viscosity is 30 cSt to 50 cSt, ii) viscosity index is 150 to 260, and iii) the pour point is less than -30 占 폚. In some embodiments, the polyalphaolefins may have RPVOT in the presence of 0.5 wt% Naugalube (R) APAN antioxidant for at least 2,100 minutes, measured according to ASTM D2272. In another embodiment, the polyalphaolefin has a Bernoulli index of less than 1.65; Alternatively, may be further specified in the range of 1.4 +/- 0.25. In still other embodiments, the PAO may be further characterized by discernible crystallization defects as measured by differential scanning calorimetry according to ASTM D 3418. Other embodiments of the PAO will be apparent in light of this disclosure.

In another non-limiting embodiment, the present invention provides a PAO produced from alpha olefin monomers consisting essentially of C ₈ normal alpha olefins, wherein the PAO comprises: a) less than 0.5% by weight hydrogenated alpha olefin monomer, b) % Hydrogenated dimer, and c) greater than 88 wt.% Hydrogenated heavy oligomer; i) 100 占 폚 kinematic viscosity is 80 cSt to 140 cSt, ii) viscosity index is 150 to 260, and iii) the pour point is less than -30 占 폚. In some embodiments, the polyalphaolefins may have RPVOT in the presence of 0.5 wt% Naugalube (R) APAN antioxidant for at least 2,000 minutes measured according to ASTM D2272. In another embodiment, the polyalphaolefin has a Bernoulli index of less than 3; Alternatively, it may be in the range of 1.1 + 0.4. In still other embodiments, the PAO lacks identifiable crystallization as measured by differential scanning calorimetry according to ASTM D 3418. Other embodiments of the PAO will be apparent in light of this disclosure

In an embodiment, the alpha olefin oligomer may be an alpha olefin oligomer produced according to any of the alpha olefin oligomer production methods described herein. In some embodiments, the heavy oligomer product may be a heavy oligomer product that is produced according to any of the heavy oligomer production methods described herein. In another embodiment, the PAO may be PAO produced according to any of the PAO production methods described herein.

Lubricant composition

The present invention also provides a new synthetic lubricant comprising PAO as described herein and / or prepared according to the process described herein. The PAOs described herein and / or prepared according to the process of the present invention are also useful in lubricant compositions and as viscosity modifiers. The PAOs described herein and / or prepared according to the present process may be used as a single base oil or may be used in combination with other base oils (e.g., mineral oils and / or other polyalphaolefins). Lubricant compositions using the PAOs described herein and / or prepared according to the process of the present invention may be used in combination with various additives. The lubricant composition or viscosity modifier may be substantially made up of the PAOs described herein and / or prepared according to the process of the present invention without additives. Alternatively, the lubricant composition or viscosity modifier may comprise any of the PAOs described herein and / or prepared according to the present process and any additives described herein. Additives that may be used with any of the PAOs described herein include, but are not limited to, metal deactivators, detergents, dispersants, antioxidants, and the like.

While not intending to be bound by theory, in some aspects, the PAO made by the present invention has a high viscosity index combined with a relatively low pour point than other properties. These properties are particularly useful in lubricant compositions and are desirable as viscosity modifiers. In this embodiment, any of the PAOs described herein and / or the PAOs made by the present invention may be used as a base oil or as a viscosity modifier in a lubricant composition. In embodiments, the PAOs described herein and / or the PAOs made by the present invention may be used in a single base oil or in mixtures with other base oils. In embodiments, the PAOs described herein and / or the PAOs made by the present invention can be used in combination with various additives. For example, any of the PAOs described herein and / or the PAOs made by the present invention can be used as a base oil in a lubricant composition or viscosity modifier; Alternatively, as a base oil in a lubricant composition; Alternatively, it can be used as a viscosity modifier. In embodiments, the lubricant composition or viscosity modifier composition may comprise any of the PAOs described herein and / or the PAOs made by the present invention and at least one additive. In an embodiment, the at least one additive is selected from the group consisting of metal deactivators, detergents, dispersants (e.g., boronated or non-borated dispersants), viscosity index improvers, viscosity modifiers, antioxidants, corrosion inhibitors, pour point depressants, An antifoaming agent, an antifoaming agent, a polysulfide component, a lubricating viscosity oil, a phosphorus-containing acid, a phosphorus-containing salt, a phosphorus-containing ester, or any combination thereof.

In some embodiments, metal deactivators that may be used include, but are not limited to, benzotriazole derivatives ("benzotriazole-based compounds"), 1,2,4-triazole, benzimidazole, Benzimidazole, 2-alkyldithiobenzothiazole, 2- ( N, N -dialkyldithiocarbamoyl) benzothiazole, 2,5-bis (alkyl-dithio) Thiadiazole, 2,5-bis ( N, N -dialkyldithiocarbamoyl) -1,3,4-thiadiazole, 2-alkyldithio-5-mercaptothiadiazole, Or any combination thereof. For example, in one embodiment, the metal deactivator is a benzotriazole derivative. In one embodiment, the metal deactivator is 2,5-bis (alkyl-dithio) -3,4-thiadiazole. The metal deactivator may be used alone or in combination with other metal deactivators in the lubricant composition. The hydrocarbyl derivatives of benzotriazole can be substituted at substitutable ring positions, for example hydrocarbyl substituted at 1-, 4-, 5-, 6-, or 7-positions, or combinations thereof at these positions ≪ / RTI > The hydrocarbyl group is typically a C ₁ to C ₃₀ hydrocarbyl group; Alternatively, a C ₁ to C ₁₅ hydrocarbyl group; Alternatively, a C ₁ to C ₁₀ hydrocarbyl group; Or alternatively a C ₁ to C ₇ hydrocarbyl group. Hydrocarbyl groups can be used without limitation to benzotriazole derivatives described herein and including hydrocarbyl groups. In one embodiment, the metal deactivator is tolyltriazole. In one aspect, suitable metal deactivators useful in the lubricant compositions of the present invention are provided in U.S. Patent Application Publication No. 20040259743, which is incorporated herein by reference.

In embodiments, suitable metal deactivators can be, but are not limited to, 2,5-bis (alkyl-dithio) -1,3,4-thiadiazole. The alkyl group of 2,5-bis (alkyl-dithio) -1,3,4-thiadiazole is a C ₁ to C ₃₀ alkyl group; Otherwise, a C ₂ to C ₂₅ alkyl group; Alternatively, a C ₃ to C ₂₀ alkyl group; Or alternatively may be a C ₄ to C ₁₅ alkyl group. The alkyl group is not limited to 2,5-bis (alkyl-dithio) -1,3,4-thiadiazole described herein and may be applied. In some embodiments, the 2,5-bis (alkyl-dithio) -1,3,4-thiadiazole is selected from the group consisting of 2,5-bis (tert-octyldithio) 4-thiadiazole, 2,5-bis (tert-decyldithio) -1,3,4-thiadiazole Sol, 2,5-bis (tert-undecyldithio) -1,3,4-thiadiazole, 2,5-bis (tert-dodecyldithio) -1,3,4- , 2,5-bis (tert-tridecyldithio) -1,3,4-thiadiazole, 2,5-bis (tert-tetradecyldithio) -1,3,4-thiadiazole, 2 (Tert-pentadecyl-dithio) -1,3,4-thiadiazole, 2,5-bis (tert-hexadecyldithio) -1,3,4-thiadiazole-, 2 (Tert-heptadecyldithio) -1,3,4-thiadiazole, 2,5-bis (tert-octadecyldithio) -1,3,4-thiadiazole, 2,5 -Bis (tert-nonadecyldithio) -1,3,4-thiadiazole, 2,5-bis (tert-icosyldithio) -1,3,4-thiadiazole, and mixtures thereof Lt; / RTI > In another embodiment, the metal deactivator may be 2,5-bis (tert-nonyldithio) -1,3,4-thiadiazole. The metal deactivator is present in the composition in an amount of from 0.0001 to 5% by weight of the lubricant composition; Alternatively 0.0003 to 1.5% by weight; Alternatively 0.0005 to 0.5% by weight; Alternatively 0.001 to 0.2% by weight. Also for example, other suitable metal deactivators include, but are not limited to, gallic ester-based compounds. In one embodiment, for example, the metal deactivator may be benzotriazole, tolyltriazole, or a combination thereof. In another embodiment, a suitable metal deactivator may be IRGAMET ™ 39, manufactured by Ciba Specialty Chemicals Corporation.

The detergents that may be used in the present lubricant compositions include, but are not limited to, metal-containing (or "metallic") detergents. Metallic detergents include oil-soluble neutral or overbased salts of alkaline or alkaline earth metals with one or more of the following acidic substances (or any combination thereof): (1) sulfonic acid, (2) carboxylic acid, (3) salicylic acid , (4) an alkyl phenol, (5) a sulfurized alkyl phenol, and (6) an organic phosphorous acid having at least one carbon-carbon double bond. Organic phosphorous acid can be prepared by reacting an olefin polymer (e. G., Polyisobutyl with a molecular weight of about < RTI ID = 0.0 > 1,000) < / RTI > with a phosphorylating agent such as phosphorus trihechloride, phosphorus pentasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, Lt; RTI ID = 0.0 > Rhen). ≪ / RTI > In another embodiment, the detergent that may be used in the lubricant composition of the present invention is a metal, especially an alkali or alkaline earth metal; Otherwise, an alkali metal; Or alternatively, the utility and neutralization of alkaline earth metals and sulfonates, phenates, sulfates, thiophosphates, salicylates, and naphthenates and other useful carboxylates. In some embodiments, the metal is selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, or barium; Alternatively, lithium, sodium, or potassium; Otherwise, magnesium, calcium, or barium; Otherwise, lithium; Otherwise, sodium; Otherwise, potassium; Otherwise, magnesium; Otherwise, calcium; Alternatively, it may be barium.

In one embodiment, any of the PAOs described herein and / or any of the detergents used in the lubricant composition or viscosity modifier composition, including the PAOs made by the present invention, may contain alkali metal detergents, alkaline earth metal detergents, Mg, Be, Sr, Na , Transient detergents including metal compounds of Ca and K, or any combination thereof; Alternatively, alkali metal detergents; Otherwise, an alkaline earth metal detergent; Alternatively, it may be an excess cleaner containing metal compounds of Mg, Be, Sr, Na, Ca and K. [ In some embodiments, the detergent comprises an excess calcium detergent. In some embodiments, any of the PAOs described herein and / or any of the detergents used in the lubricant compositions or viscosity modifier compositions, including the PAOs made by the present invention, may be present in the form of a phenolic acid salt, a carboxylic acid salt, a sulfonic acid salt, Salixarate, calixarate, saliginen, or any combination thereof.

The term "transient ", used in the context of metallic detergents, is used to denote metal salts in which the metal is present in a stoichiometrically excessive amount of organic radicals. Conventional methods of preparing the over-salt salt include heating a mineral oil solution of an acid and stoichiometrically excess metal neutralizing agent such as metal oxides, hydroxides, carbonates, bicarbonates, or sulfides, and filtering the product. "Accelerators" used to contain excess metal in the neutralization stage are known. Examples of compounds useful as accelerators include phenolic materials such as phenol, naphthol, alkylphenol, thiophenol, alkylphenol sulfides, and condensation products of formaldehyde and phenolic materials, alcohols such as methanol, 2 (Such as propylene, octanol, 2-ethoxyethanol, diethylene glycol ethers, ethylene glycol, stearyl alcohol, and cyclohexyl alcohol), and amines (such as aniline, phenylenediamine, phenothiazine, Beta-naphthylamine, and dodecylamine). For example, one method of producing a basic salt comprises a step of mixing an acid and an excess of a basic alkaline earth metal neutralizing agent and at least one alcohol promoter, and a mixture carbonization step at a high temperature such as 60 ° C to 200 ° C.

Examples of suitable metal-containing detergents include, but are not limited to, neutral sodium sulphate, transient sodium sulphate, sodium carboxylate, sodium salicylate, sodium phenolate, sodium sulphate phenolate, lithium sulphonate, lithium carboxylate, Wherein the magnesium salt is at least one selected from the group consisting of sodium salt, lithium salt, lithium salicylate, lithium phenate, lithium sulfoxide, calcium sulfonate, calcium carboxylate, calcium salicylate, calcium phenolate, calcium sulfinate, magnesium sulfonate, magnesium carboxylate, magnesium salicylate, Wherein the metal salt is at least one selected from the group consisting of magnesium sulfate, magnesium sulfate phenolate, potassium sulfonate, potassium carboxylate, potassium salicylate, potassium phenolate, potassium sulfide phenolate, zinc sulfonate, zinc carboxylate, zinc salicylate, And neutral and transient salts of materials such as acid salts. Also exemplified are hydrolyzed phosphorus sulfide olefins having from 10 to 2,000 carbon atoms or hydrolyzed phosphorus sulfide alcohols having from 10 to 2,000 carbon atoms and / or calcium, lithium, sodium, potassium, and mixtures of aliphatic-substituted phenolic compounds Magnesium salts. Also included by way of illustration are calcium, lithium, sodium, potassium, and magnesium salts of aliphatic carboxylic acids and aliphatically substituted cycloaliphatic carboxylic acids and similar alkali and alkaline earth metal salts of many other useful organic acids. Mixtures of neutral or transient salts of two or more different alkali and / or alkaline earth metals may be used. Similarly, neutral and / or transdermal salts of two or more different acid mixtures may be used.

As is known, transient metal detergents are generally considered to contain transient inorganic bases in the form of micro-dispersions or colloidal suspensions. Thus, the term "oil-souble ", when applied to metallic detergents, is such that the inorganic bases are either completely or sufficiently fat soluble in the terminological sense to the extent that such detergents behave sufficiently Is intended to include non-metallic detergents. Collectively, the various metallic detergents referred to herein are sometimes referred to as neutral, basic, or transient alkali metal or alkaline earth metal-containing organic acid salts.

Utility neutral and over metallic detergents and alkaline earth metal-containing detergents and methods of manufacture are among other things the same as those described in U. S. Patent Nos. 2,001,108, 2,081,075, 2,163,622, 2,270,183, 2,292,205, 2,335,017, 2,399,877, 2,416,281, 2,451,345, 2,451,346, 2,485,861, 2,501,731, 2,501,732 in, 2.58552 million, 2,671,758, 2,616,904, 2,616,905, 2,616,906, 2,616,911, 2,616,924, 2,616,925, 2,617,049, 2.69591 million, 3178368, 3367867, 3496105, 3629109, 3865737, 3907691, 4100085, 4129589, 4137184, 4.18474 million, 4,212,752, 4,617,135, 4,647,387, and 4.88055 million .

The metallic detergents that can be used in the present invention are preferably oil boron neutralized and / or transient alkali or alkaline earth metal-containing detergents. Methods of making boronated metallic detergents are described, among other things, in U.S. Patent Nos. 3,480,548, 3,679,584, 3,829,381, 3,909,691, 4,965,003, and 4,965,004. Additional detergents which are generally useful in lubricants include, among others, phenolates / salicylates, sulfonates / phenolates, sulfonates / salicylates, sulfonates, as described in U.S. Patent Nos. 6,153,565, 6,281,179, 6,429,178, and 6,429,179. / "Hybrid" formulated with mixed surfactant systems such as phenolate / salicylate.

The detergent may be present in the lubricant composition in any desired or effective amount. In one aspect, the lubricating component is present in an amount of 0.01% to 0.8% by weight, based on the total weight of the lubricating composition; Alternatively 0.05% to 0.6% by weight; Alternatively, from 0.09% to 0.4% by weight can be included. In one embodiment, the additive composition comprises 0.06% to 5% by weight, based on the total weight of the lubricating composition; Otherwise, 0.30% to 3.6%; Alternatively, from 0.54% to 2.38% by weight. However, one of skill in the art will appreciate that any amount can be used in the lubricant composition.

By way of example in one embodiment, suitable dispersing agents for use in lubricant compositions include, but are not limited to, basic nitrogen-containing, non-carbon dispersing agents. Suitable non-cationic dispersing agents include, but are not limited to, hydrocarbylsuccinimides, hydrocarbylsuccinamides, mixed esters / amides of hydrocarbyl-substituted succinic acids (e.g., stepwise and hydrocarbyl- Amine mixtures, and / or amino alcohols), Mannich condensation products (such as those formed from hydrocarbyl-substituted phenols, formaldehyde and polyamines), and high molecular weight aliphatic or alicyclic halides And an amine dispersant formed by reaction with an amine (e.g., a polyalkylene polyamine). Combinations or mixtures of any of these dispersants may also be used.

Such dispersant preparation methods are well known and are found in the following references. For example, hydrocarbyl-substituted succinimides and succinamides and methods for their preparation are among others described in U.S. Patent Nos. 3,018,247, 3,018,250, 3,018,291, 3,172,892, 3,185,704, 3,219,666, 3,272,746, 3,361,673, and 4,234,435. Mixed ester-amides of hydrocarbyl-substituted succinic acids are described, for example, above in U.S. Patent Nos. 3,576,743, 4,234,435, and 4,873,009. Mannich dispersants which are condensation products of hydrocarbyl-substituted phenols, formaldehyde and polyamines are more preferred than any of their patents, for example, in U.S. Patent Nos. 3,368,972, 3,413,347, 3,539,633, 3,697,574, 3,725,277, 3,725,480, 3,726,882, 3,798,247, 3,803,039, 3,985,802, 4,231,759, and 4,142,980. Amine dispersants and methods for their preparation from high molecular weight aliphatic or alicyclic halides and amines are among others described in, for example, U.S. Patent Nos. 3,275,554, 3,438,757, 3,454,555, and 3,565,804.

In one aspect and broadly, basic nitrogen or basic nitrogen, including amines of the type described in U.S. Patent No. 4,235,435, and furthermore, amines having at least one hydroxyl group, are applied to formulate dispersants suitable for use herein. The amine can be a polyamine such as a polyalkylene polyamine, a hydroxy-substituted polyamine and a polyoxyalkylene polyamine. The polyalkylene polyamine may include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and dipropylenetriamine. Pure polyethylene polyamines as well as mixtures of linear, branched and cyclic polyethylene polyamines having an average of from 2 to 7 nitrogen atoms per molecule, such as from 3 to 5 nitrogen atoms per molecule, may be used. Hydroxy-substituted amines include, but are not limited to, N -hydroxyalkyl-alkylene polyamines such as N - (2-hydroxyethyl) ethylenediamine, N- (2- hydroxyethyl) N -hydroxyalkylated alkylenediamines of the type described in U.S. Patent No. 4,873,009. Typical polyoxyalkylene polyamines include polyoxyethylene and polyoxypropylene diamines having an average molecular weight of 200 to 2500 and triamines.

In one embodiment, the at least one dispersing agent may comprise a hydrocarbyl substituent, for example an olefinic hydrocarbon. Non-limiting examples of suitable olefinic hydrocarbons include isobutene. The isobutylene used may be a stream containing isobutylene which is produced by decomposing the hydrocarbon stream to produce a hydrocarbon mixture consisting essentially of C ₄ hydrocarbons. For example, it produces a thermal cracking process C ₄ classifier (cuts) which (stream separation device) to C ₄ paraffins and C ₄ olefins, most components including isobutene. Butadiene and acetylene are substantially removed from the stream by an additional selective hydrogenation or extractive distillation process. The product stream is referred to as "additional balance I" and is suitable for polyisobutylene (PIB) synthesis and typically has the following composition: 44-49% isobutene, 24-28% 1-butene, 19-21% 2 Butene, 6-8% n-butane, 2-3% isobutane. The components of the additional balance I stream may vary depending on operating conditions. The additional balance I stream can be purified to produce a substantially pure isobutene product, i. E., A product substantially consisting of isobutene.

Antioxidants that may be used in the lubricant composition include, but are not limited to, amine-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants. Amine-based antioxidants include, but are not limited to, monoalkyldiphenylamine-based compounds (such as monooctyldiphenylamine and monononyldiphenylamine), dialkyldiphenylamine-based compounds 4,4'-dibutyldiphenylamine, 4,4'-dibutyldiphenylamine, 4,4'-dipentyldiphenylamine, 4,4'-dioctyldiphenylamine, , And 4,4'-dinonyldiphenylamine), polyalkyldiphenylamine-based compounds (such as tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetraoctyldiphenylamine, and tetranonyldiphenylamine ), And naphthylamine-based compounds (e.g., alpha-naphthylamine, phenyl-alpha-naphthylamine, butylphenyl- alpha -naphthylamine, pentylphenyl- alpha -naphthylamine, Naphthylamine, heptylphenyl-alpha-naphthylamine, octylphenyl-alpha-naphthylamine, and nonylphenyl-alpha-naphthylamine). Phenol-based antioxidants include, but are not limited to, monophenol-based compounds such as 2,6-di-tert-butyl-4-methylphenol and 2,6-di- ), And diphenol-based compounds such as 4,4'-methylenebis (2,6-di-tert-butylphenol) and 2,2'-methylenebis Phenol)). Sulfur-based antioxidants include but are not limited to phenothiazine, pentaerythritol-tetrakis (3-laurylthiopropanate), bis (3,5-tert-butyl-4-hydroxybenzyl) Di (tert-butyl-4-hydroxyphenyl) propionate and 2,6-di-tert-butyl-4- (4,6- ) -1,3,5-triazine-2-methylamino) phenol. In one embodiment, each of these antioxidants may be used alone or in any combination of two or more.

In one embodiment, the PAO described herein and / or the PAO-containing lubricant composition or any of the anti-emulsifiers used in the viscosity modifier composition is selected from the group consisting of propylene oxide derivatives, ethylene oxide derivatives, polyoxyalkylene alcohols, , Alkoxylated amino alcohols, alkoxylated diamines, alkoxylated polyamines polyethylene glycols, polyethylene oxides, polypropylene oxides, glycolic monooleates, hypercalcium sulfonates, 1- Hydroxyethyl) -2-alkenylimidazoline, fatty acid alkylamine contact products, alkoxylated alkylphenol formaldehyde resin solutions, alkoxylated polyglycols, or any combination thereof. In embodiments, the alkoxylated compound used as the anti-emulsifier can be ethylene oxide, substituted ethylene oxide (e.g., propylene oxide), alkoxylate of polyene oxide, or any combination thereof.

In one embodiment, the PAOs described herein and / or any of the polysulfide components used in the lubricant compositions or PAO-containing viscosity modifier compositions made by the present invention can be olefin sulfides, oligomeric sulfur species, dialkyl tri sulfide Compounds, dialkyl tetrasulfide compounds, substituted thiadiazoles, 2- ( N, N -dialkyldithiocarbamoyl) -benzothiazole, 2,5-bis (alkyldithio) -1,3,4 ( N, N -dialkyldithiocarbamoyl) -1,3,4-thiadiazole, 2,5-bis (tert-nonyldithio) 4-thiadiazole, 2-alkyldithio-5-mercaptothiadiazole, methylsulfate of oleic acid, alkylphenol sulfide, dipentene sulfide, dicyclopentadiene sulfide, terpene sulphide, diels- Diels-Alder adducts, phosphorus sulfide hydrocarbons, or any combination thereof.

In one embodiment, the PAO described herein and / or the PAO-containing lubricant composition produced by the present invention or any defoamer used in the viscosity modifier composition may be a copolymer of ethyl acrylate and 2-ethylhexyl acrylate, a vinyl acetate monomer (Ethylene oxide-propylene oxide) polymer, polyacetal silicon, silicon of dimethylsilicone, polysiloxane, polyacrylate polyethylacrylate, poly-2-ethylhexyl acrylate, Polyvinyl acetate, 2-ethylhexyl acrylate / ethyl acrylate copolymer, polydimethyl / siloxane, or any combination thereof.

In one embodiment, any of the phosphorus-containing acids, phosphorus-containing salts, or phosphorus-containing esters used in the lubricant compositions or viscosity modifier compositions, including the PAOs and PAOs described herein and / or prepared by the present invention, (Heptyl) dithiophosphate, zinc di- (octyl) dithiophosphate di (amyl) dithiophosphate, zinc di- (Dodecyl) dithiophosphate, zinc di- (decyl) dithiophosphate, zinc di- (decyl) dithiophosphate, zinc di- (Amine salts of phosphorus-containing ethers, amine salts of phosphorus-containing ethers, amine salts of phosphorus-containing carboxylic esters, amine salts of phosphorus-containing ethers, Amine salts of phosphorus-containing amides, partial S Zinc dialkyldithiophosphate derived from a mixture of phosphorous acid, amyl alcohol and isobutyl alcohol, zinc dialkyl dithiophosphate derived from a mixture of 2-ethylhexyl alcohol and isopropyl alcohol, 4-methyl-2-pentanol and iso A zinc dialkyl dithiophosphate derived from a propyl alcohol mixture, or any combination thereof.

Catalyst System and Catalyst System Component

The present invention includes a catalyst system, a method for preparing a catalyst system, an oligomerization method using a catalyst system, and a method for producing a polyalphaolefin using the catalyst system. The disclosed catalyst systems generally include a metallocene component and an activator component. For example, the catalyst system comprises at least one metallocene and at least one activator; Alternatively, the catalyst system comprises at least one metallocene, at least one first activator, and at least one second activator. The present invention also encompasses an oligomerization process comprising: a) contacting a catalyst system having an alpha olefin monomer and a metallocene; and b) forming an oligomer product in oligomerization conditions. In one embodiment, the oligomerization comprises: a) contacting a catalyst system having an alpha olefin monomer and a metallocene; b) forming an oligomer product at the oligomerization condition; and c) contacting the oligomer product to provide a heavy oligomer product. And a reactor effluent separation step. In some embodiments, the catalyst system comprises a metallocene and an activator; Or alternatively, a metallocene and activator combination. In another embodiment, the catalyst system may comprise a metallocene, a first activator, and a second activator. In another embodiment, the activator may also be substantially absent in the catalyst system.

Broadly, alpha olefin monomers, catalyst systems, metallocenes, activators (first, second, or other), oligomer products, oligomerization conditions, and heavy oligomer products are independent components of the oligomerization process, . The oligomerization process and any process involving the oligomerization process can be carried out using any of the alpha olefin monomers described herein, the catalyst systems described herein, the metallocenes described herein, the activators described herein (first, second, or the like) May be described by applying any combination of the oligomer product described herein, the oligomerization conditions described herein, and the heavy oligomer product described herein.

When the activator is used in a catalyst system, the activator (first, second, or other) may comprise a solid oxide chemically treated with an electron attracting anion; Alternatively, the activator (first, second, or other) may comprise alumoxane. In some embodiments, the catalyst system may comprise a metallocene, a first activator comprising a solid oxide chemically treated with an electron attracting anion, and a second activator. In another embodiment, the catalyst system may comprise a metallocene, a first activator comprising alumoxane, and a second activator.

Any number of pre-contact or post-contact steps may be applied prior to the alpha olefin oligomer product formation step in oligomerization conditions, when the optionally selected catalyst system component and / or alpha olefin monomer is pre-contacted and / or post-contacted. Any of the alpha olefin monomers, metallocenes, activators, solid oxides, or electron withdrawing anions that can be pre-contacted for some time prior to the alpha olefin and catalyst system contacting steps in any embodiment or embodiment of the oligomerization methods described herein , Or any other activator or combination of activators may be applied. Each component that can be used in the catalyst system is described independently herein.

In one embodiment and in certain embodiments described herein, the oligomerization method (s) described herein may be included in the polyalphaolefin production process. In a non-limiting embodiment, the polyalphaolefin production process comprises the steps of: a) contacting a catalyst system having an alpha olefin monomer and a metallocene, b) forming an oligomer product in oligomerization conditions, c) providing a heavy oligomer product A reactor effluent separation step comprising an oligomer product, and d) a hydrogenation step of a heavy oligomer product to provide a polyalphaolefin.

Metallocene

In one aspect, the present invention provides a catalyst system comprising a metallocene. In an embodiment, a metallocene combination may be applied to the catalyst system. When multiple metallocenes are applied, the metallocene can be referred to as a first metallocene (or metallocene compound) and a second metallocene (or metallocene compound). In another embodiment, two different metallocenes can be used simultaneously in an oligomerization process to produce an alpha olefin product.

Throughout this disclosure, metallocenes are generically referred to as Group I ligands, Group II ligands, and Groups 4, 5, or 6 metals; Alternatively, Group I ligands, Group II ligands, and Group IV metals; Alternatively, Group I ligands, Group II ligands, and Group 5 metals; Or alternatively, Group I ligands, Group II ligands, and Group VI metals. In one embodiment, the metal of the metallocene may be Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, or W. In another embodiment, the metal of the metallocene is selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten; Alternatively, titanium, zirconium, hafnium, or vanadium; Alternatively, titanium, zirconium, or hafnium; Otherwise, titanium; Otherwise, zirconium; Otherwise, hafnium; Alternatively, it may be vanadium.

In one embodiment, the Group I ligand of the metallocene is a pi-linkage? ^X ? ⁵ ligand. The pi-linked eta ^x > ⁵ ligands used as the Group I ligands of the present invention are used in eta ^{5 -cycloalkadiene} yl-type ligands, eta ⁵ -cycloalkadiene yl-type ligand analogs, and "open metallocenes"Lt; RTI ID = 0.0 > ⁵ -alkadienyl-type < / RTI > In an embodiment, the metallocene used in any embodiment or embodiment of the present invention comprises at least one η ⁵ -cycloalkadienyl-type or η ⁵ -alkadienyl-type ligand. In some embodiments, I group ligand is η ⁵ - cyclopentadienyl, η ^5-indenyl, η ^5-fluorenyl, η ^5-alkyne diene-yl -, η ⁶ - borate benzene-ligand, and their Substituted < / RTI > analogs. Other aspects and illustrations of group I ligands are described herein and may be used to describe metallocenes that may be used in any of the embodiments or examples described herein without limitation. With respect to the unsaturated ligand linkage to the metallocene metal, such ligands are denoted to include ligands which are linked according to the conventional eta ^x (eta-x) nomenclature, where x is coordinated to the transition metal or, for example, 18- is an integer corresponding to the number of atoms expected to coordinate according to the electronic rules. Group I ligands may be substituted or non-substituted.

According to another aspect, the group I ligand is η ⁵ - can include at least one of the heterocyclic ring fused to the type of ligand-cyclopropyl alkyne diene-yl-type or η ⁵ - alkyne diene days. In some embodiments, for example, group I ligand is η ⁵ - cyclopentadienyl ligands, η ⁵ - indenyl ligand, or heterocyclic be similar to Group I ligands, including clicking residues drop in the fused their substituted analogues . Examples of fused heterocyclic residues include, but are not limited to, pyrrole, furan, thiophene, phosphol, imidazole, imidazoline, pyrazole, pyrazoline, oxazole, oxazoline, isoxazole, isoxazoline, Thiazoles, thiazolines, isothiazolines, and the like, and include partially saturated analogs of these rings.

In one aspect, the group II ligands of a metallocene are typically circular and not the ligand binding η ^{x ≥5} sigma-binding ligands pi bonded to the metal by the ligand binding and η ^{x <5} bonding form. Therefore, η ^{x <5-binding} ligands are typically sigma-bonded halides, sigma-bonded hydride, Sigma-bonded hydrocarbyl ligand (e.g., above all alkyl and alkenyl ligands), and η ^{x <5} "pie - comprises one alkyne diene, and other like-binding "ligand e.g. ^x η ^{<η 5} bonding form to ² is coupled to a metal-alkene, η ^3-allyl, η ^4. Therefore, the metallocene group II ligands of the invention sigma metallocene-binding ligands and η ^{5-cyclopropyl} alkyne diene-yl-type ligand and the metal associated with typical metallocene hwahapmulwa other pi-bonded ligand, η ^x non ^≥5 Some pi-binding ligands are included. Examples and examples of Group II ligands are provided herein.

In one embodiment, the metallocene may comprise two Group I ligands. In this embodiment, and in certain embodiments, the metallocene may comprise two Group I ligands, wherein the two Group I ligands are connected to a linking group; Alternatively, the two Group I ligands are separated (unlinked or non-ligated). The linking group is considered as a substituent in the Group I ligand so that the connected Group I ligand can be further substituted with other non-linking substituents or non-substituted except for the linking group. Thus, Group I ligands can be linked and more substituted, linked and more non-substituted, non-linked and non-ligated, or non-linked and more non-substituted; Alternatively, Group I ligands may be linked and further substituted; Alternatively, Group I ligands may be linked and more non-substituted; Alternatively, Group I ligands may be substituted with non-linking and non-linking ligands; Alternatively, Group I ligands can be non-linked and more non-substituted. Also in certain embodiments, the metallocene can comprise a Group I ligand and at least one Group II ligand, wherein Group I ligands and Group II ligands are connected to a linking group; Alternatively, Group I ligands and Group II ligands are separated without being connected by a linking group.

In an embodiment, and in certain embodiments, the metallocene may have the formula X ²¹ X ²² X ²³ X ²⁴ M ^l _. In this embodiment, X ²¹ , X ²² , X ²³ , X ²⁴ , and M ¹ are independently described herein and apply in any combination to describe a metallocene having the formula X ²¹ X ²² X ²³ X ²⁴ M ¹ . In some embodiments, M ^l is 4, 5, or 6 metals; Otherwise, a Group 4 metal; Otherwise, a Group 5 metal; Or alternatively, a Group 6 metal. In another embodiment, M ^l is Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, or W; Alternatively, Ti, Zr, or Hf; Alternatively, V, Nb, or Ta; Alternatively, Cr, Mo, or W; Alternatively, Ti, Zr, Hf, or V; Alternatively, Ti, Zr, or Hf; Otherwise, Ti; Otherwise, Zr; Otherwise, Hf; Or otherwise. In an embodiment, X ²¹ is an I group ligand, X ²² is an I group ligand or a II group ligand, and X ³ and X ⁴ are independently group II ligands; Unless otherwise noted, X ²¹ and X ²² are independently group I ligands not linked by a linking group, and X ²³ and X ²⁴ are independently group II ligands; X ²¹ and X ²² are independently an I group ligand connected by a linking group, and X ²³ and X ²⁴ are independently group II ligands; Or alternatively, X ²¹ is an I group ligand and X ²² , X ²³ , and X ²⁴ are independently a substituted or non-substituted hydrocarbyl group having 1 to 20 carbon atoms. In an ^{embodiment, X 21, X 22, X} 23, and X a substituent of ²⁴ is independently halide, C ₁ to C ₂₀ hydrocarbyl carboxy deugi, C ₁ to C ₂₀ aliphatic groups, C ₁ or C ₂₀ heterocyclic group , A C ₆ or C ₂₀ aromatic group, a C ₁ or C ₂₀ heteroaromatic group, an amido group, a C ₁ or C ₂₀ N -hydrocarbylamido group, a C ₁ or C ₂₀ N, an N -dihydrocarbylamido group, A C ₁ or C ₂₀ hydrocarbyl thiolate group, or a C ₃ or C ₃₀ trihydrocarbylsiloxy group.

In a non-limiting embodiment, the metallocene may have the formula:

X ²¹ X ²² X ²³ X ²⁴ M ¹ ; From here:

M ¹ is selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten;

X ²¹ is an I group ligand;

X ²² is an I group ligand or a II group ligand; And

X ²³ and X ²⁴ are independently selected from Group II ligands. In some embodiments, X ²¹ and X ²² are connected by a connector. In another embodiment, X ²¹ and X ²² are not connected by a linker.

In some non-limiting embodiments, the metallocene may have the formula:

X ²¹ X ²² X ²³ X ²⁴ M ^l : Here:

M ¹ is independently selected from Ti, Zr, or Hf;

X ²¹ and X ²² are Group I ligands connected by a linking group; And

X ²³ and X ²⁴ are independently selected from Group II ligands.

In other non-limiting embodiments, the metallocene may have the formula:

X ²¹ X ²² X ²³ X ²⁴ M ^l : Here:

M ¹ is independently selected from Ti, Zr, or Hf;

X ²¹ and X ²² are Group I ligands not connected by a linking group; And

X ²³ and X ²⁴ are independently selected from Group II ligands.

In another non-limiting embodiment, the metallocene may have the formula:

X ²⁵ X ²⁶ X ²⁷ X ²⁸ M ² ; From here

M ² is Ti, Zr, Hf, or V;

X ²⁵ is an I group ligand;

X ²⁶ , X ²⁷ , and X ²⁸ are independently a substituted or non-substituted hydrocarbyl group having 1 to 20 carbon atoms; And here

^{X 25, X 26, X 27} , and the optional substituents of X ²⁸ are independently a halide, C ₁ to C ₂₀ hydrocarbyl carboxy deugi, C ₁ to C ₂₀ aliphatic groups, C ₁ to C ₂₀ heterocyclic group, C ₆ to C ₂₀ aromatic group, C ₁ to C ₂₀ heteroaromatic group, an amido group, C ₁ to C ₂₀ N - hydrocarbyl amido group, C ₁ to C ₂₀ N, N - di-hydrocarbyl amido group, C ₁ to C ₂₀ hydrocarbyl thiolate group, and a C ₃ to C ₃₀ trihydrocarbylsiloxy group.

In one embodiment, and in certain embodiments, the metallocene may comprise a linking group connecting a Group I ligand and another ligand (another Group I ligand or Group II ligand) at the metallocene. The linker includes a bridge, wherein the bridge includes the smallest number of consecutive atoms necessary to traverse the link between the I group ligand and the other ligand associated therewith. For example, the linking group may be substituted with one to three consecutive bridging atoms; Unlike 1 or 2 linked bridging atoms; Otherwise, a mono-bridging atom; Otherwise, two connected bridging atoms; In turn, include tri-bridging atoms. In an embodiment, each connecting bridging atom is selected from the group consisting of C, O, S, N, P, Si, Ga, Sn, or Pb; Alternatively, C, Si, Ge, or Sn; Otherwise; C or Si; Otherwise, C; Alternatively, it may be Si. The linking group is saturated, or the linking group is unsaturated; Otherwise, the connector is saturated; Alternatively, the linking group may be unsaturated.

The linking group includes, but is not limited to, a C ₁ -C ₂₀ hydrocarbyl group, a C ₀ -C ₂₀ nitrogen-linking group, a C ₀ -C ₂₀ phosphorus-linking group, a C ₁ -C ₂₀ organyl group, a C ₀ -C ₃₀ silicon- A C ₀ -C ₂₀ germanium-linking group, a C ₀ -C ₂₀ tin-linking group, or a C ₀ -C ₂₀ lead-linking group; Alternatively, a C ₁ -C ₂₀ hydrocarbyl group, or a C ₀ -C ₃₀ silicon-bonded group; Alternatively, a C ₁ -C ₂₀ hydrocarbyl group; Otherwise, a C ₀ -C ₂₀ nitrogen-linking group; Otherwise, a C ₀ -C ₂₀ in-linking group; Otherwise, a C ₁ -C ₂₀ organyl group; Otherwise, a C ₀ -C ₃₀ silicon-bond group; Otherwise, a C ₀ -C ₂₀ germanium-linking group; Otherwise, a C ₀ -C ₂₀ tin-bond group; Or alternatively, a C ₀ -C ₂₀ lead-linking group.

In some embodiments or embodiments comprising a linker, the linker comprises moieties having the formula > CR ¹ R ² ,> SiR ³ R ⁴ , or -CR ⁵ R ⁶ CR ⁷ R ⁸ - wherein R ¹ , R ^{2, R 3, R 4,} R 5, R 6, R 7, and R ⁸ are independently hydrogen, halide, C ₁ -C ₂₀ hydrocarbyl groups, C ₁ -C ₂₀ oxygen-coupler, C ₁ -C ₂₀ sulfur-coupler, C ₀ -C ₂₀ nitrogen-coupler, C ₀ -C ₂₀ a-coupler, C ₁ -C ₂₀ Organic groups, C ₀ to C ₂₀ non-small-coupler, C ₀ -C ₃₀ silicon-coupler, C ₀ A -C ₂₀ germanium-linking group, or a C ₀ -C ₂₀ tin-linking group; A C ₀ to C ₂₀ lead-bond group, a C ₀ to C ₂₀ boron-bond group, or a C ₀ to C ₂₀ aluminum-bond group. In this embodiment and in certain embodiments, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are independently saturated or unsaturated; Otherwise, saturated; Or alternatively, unsaturated. In some embodiments comprising a linking group, the linking group may have the formula &gt; CR ¹ R ² ,> SiR ³ R ⁴ , or -CR ⁵ R ⁶ CR ⁷ R ⁸ - wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are independently hydrogen, a halide, a saturated or unsaturated C ₁ -C ₂₀ aliphatic group, or a C ₆ -C ₂₀ aromatic group; Otherwise, it is selected from saturated C ₁ -C ₂₀ aliphatic groups; ^{Otherwise, R 1, R 2, R} 3, R 4, R 5, R 6, R 7, and R ⁸ are independently hydrogen, halide, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₆ -C ₂₀ aryl, or C ₆ -C ₂₀ aromatic group selected from; Is selected from hydrogen, a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ alkenyl group, or a C ₆ -C ₂₀ aryl group; Or alternatively R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently selected from hydrogen or a saturated or unsaturated C ₁ -C ₂₀ hydrocarbyl group. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ , which are described herein and used in the linking groups, are independently selected from the group consisting of hydrogen, alkyl, / &Gt; or R &lt; ^{8 &} gt ;.

In another embodiment and in certain embodiments, the Group I ligand in the metallocene is selected from the group consisting of a substituted or non-substituted η ⁵ -cycloalkadienyl-ligand, a substituted or non-substituted η ⁵ -alkadienyl- A ligand, or a substituted or non-substituted η ⁶ -borate benzene-containing ligand; Alternatively, a substituted or non-substituted cyclopentadienyl ligand, a substituted or non-substituted indenyl ligand, a substituted or non-substituted fluorenyl ligand, a substituted or non-substituted tetrahydroindenyl ligand , Substituted or non-substituted tetrahydrofluorenyl ligands, or substituted or non-substituted octahydrofluorenyl ligands; Or alternatively, a substituted or non-substituted cyclopentadienyl ligand, a substituted or non-substituted indenyl ligand, or a substituted or non-substituted fluorenyl ligand. Also, in certain embodiments, the Group I ligand in the metallocene is a substituted or non-substituted cyclopentadienyl; Alternatively, substituted or unsubstituted indenyl; Alternatively, substituted or unsubstituted fluorenyl; Alternatively, substituted or unsubstituted tetrahydroindene; Alternatively, substituted or unsubstituted tetrahydrofluorenyl; Or alternatively, substituted or unsubstituted octahydrofluorenyl. Alternatively, the metallocene may have two Group I ligands and the Group I ligand is independently selected from two substituted or non-substituted cyclopentadienyl, substituted or non-substituted fluorenyl and substituted or non- Substituted cyclopentadienyl, substituted or unsubstituted fluorenyl and substituted or non-substituted indenyl, two substituted or unsubstituted fluorenyl, or two substituted or non-substituted Lt; / RTI &gt; Alternatively, for Group I ligands, Group I ligands may be selected from independently substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, or substituted or unsubstituted fluorenyl .

As described herein, a linked Group I ligand may be further substituted or non-substituted with other non-linking substituents. Non-Linked Group I ligands can be substituted or non-substituted. In this embodiment, each non-linking substituent in the Group I ligand is independently selected from the group consisting of, but not limited to, a halide, a C ₁ to C ₂₀ hydrocarbyl group, a C ₁ to C ₂₀ hydrocarboxy group, a C ₃ to C ₂₀ heterocyclic group, C ₆ to C ₂₀ aromatic group, C ₃ to C ₂₀ heteroaromatic group, C ₁ to C ₂₀ hydrocarbyl silyl group, C ₂ to C ₄₀ di-hydrocarbyl silyl group, C ₃ to C ₆₀ tree hydrocarbyl A C ₁ to C ₂₀ N-hydrocarbylamine group (sometimes referred to as a C ₁ to C ₂₀ N -hydrocarbylamido group), a C ₂ to C ₄₀ N, N -dihydrocarbyl An amine diol (sometimes referred to as a C ₂ to C ₄₀ N, N -dihydrocarbylamido group), a C ₁ to C ₂₀ hydrocarbyl thiolate group, or a C ₃ to C ₆₀ trihydrocarbylsiloxy group; Alternatively, a halide, a C ₁ to C ₂₀ hydrocarbyl group, or a C ₁ to C ₂₀ hydrocarboxyl group; Otherwise, a halide or C ₁ to C ₂₀ hydrocarbyl group; Otherwise, a halide or C ₁ to C ₂₀ hydrocarboxy group; A C ₁ to C ₂₀ hydrocarbyl group or a C ₁ to C ₂₀ hydrocarbyl group; Otherwise, halide; Alternatively, a C ₁ to C ₂₀ hydrocarbyl group; Or alternatively a C ₁ to C ₂₀ hydrocarboxy group. In other embodiments and in certain embodiments described herein, each non-linking substituent in the Group I ligand is independently selected from, but not limited to, a halide, a C ₁ to C ₁₀ hydrocarbyl group, a C ₁ to C ₁₀ hydrocarboxy group, a C ₃ to C ₁₅ heterocyclic group, C ₆ to C ₁₅ aromatic group, C ₃ to C ₁₅ heteroaromatic group, C ₁ to C ₁₀ hydrocarbyl silyl group, C ₂ to C ₂₀ di-hydrocarbyl silyl group, C ₃ to C ₃₀ tree hydrocarbyl silyl group, an amine group, C ₁ to C ₁₀ hydrocarbyl amine N- group (sometimes C ₁ to C ₁₀ N - a hydrocarbyl amido hereinafter), C ₂ to C ₂₀ N, N -dihydrocarbylamine diol (sometimes referred to as C ₂ to C ₂₀ N, N -dihydrocarbylamido group), C ₁ to C ₁₀ hydrocarbyl thiolate group, or C ₃ to C ₃₀ trihydrocarbyl A billysiloxy group; Alternatively, a halide, a C ₁ to C ₁₀ hydrocarbyl group, or a C ₁ to C ₁₀ hydrocarboxyl group; Otherwise, a halide or C ₁ to C ₁₀ hydrocarbyl group; Alternatively, halide or C ₁ to C ₁₀ hydrocarbyl carboxyl group; In contrast, C ₁ to C ₁₀ hydrocarbyl or C ₁ to C ₁₀ hydrocarbyl carboxyl group; Otherwise, halide; Alternatively, a C ₁ to C ₁₀ hydrocarbyl group; Or alternatively a C ₁ to C ₁₀ hydrocarboxy group.

In yet another embodiment and in certain embodiments described herein, each non-linking substituent in the Group I ligand is independently selected from the group consisting of, but not limited to, a halide, a C ₁ to C ₅ hydrocarbyl group, a C ₁ to C ₅ hydrocarboxy group , A C ₃ to C ₁₀ heterocyclic group, a C ₆ to C ₁₀ aromatic group, a C ₃ to C ₁₀ heteroaromatic group, a C ₁ to C ₅ hydrocarbylsilyl group, a C ₂ to C ₁₀ dihydrocarbylsilyl group , A C ₃ to C ₁₅ trihydrocarbylsilyl group, an amine group, a C ₁ to C ₅ N-hydrocarbylamine group (sometimes referred to as a C ₁ to C ₅ N -hydrocarbylamido group), a C ₂ to C ₁₀ N, N - di-hydrocarbyl amine group (sometimes C ₂ to C ₁₀ N, N - di-hydrocarbyl referred to as an amido group), C ₁ to C ₅ hydrocarbyl thio acrylate group, or a C ₃ to C ₁₅ A trihydrocarbylsiloxy group; Alternatively, a halide, a C ₁ to C ₅ hydrocarbyl group, or a C ₁ to C ₅ hydrocarboxy group; Alternatively, a halide or C ₁ to C ₅ hydrocarbyl group; Otherwise, a halide or C ₁ to C ₅ hydrocarboxy group; In contrast, C ₁ to C ₅ hydrocarbyl group or a C ₁ to C ₅ hydrocarbyl carboxyl group; Otherwise, halide; Alternatively, a C ₁ to C ₅ hydrocarbyl group; Or alternatively a C ₁ to C ₅ hydrocarboxy group.

In an embodiment, each halide substituent used as a halide for a non-linking substituent in the Group I ligand or for a linking group may be independently a fluoride, chloride, bromide, or iodide. In an embodiment, the halide used in each halide substituent or linkage group used as a non-linking substituent in the Group I ligand is independently a fluoride; Otherwise, chloride; Otherwise, bromide; Or alternatively it may be iodide.

In embodiments, the hydrocarbyl group in the Group I ligand, the non-linking substituent, the hydrocarbyl group used in the linking group, or the hydrocarbyl group in the non-linking substituent in the Group I ligand (such as a trihydrocarbylsilyl group, N, N -dihydrocarbylamine, or hydrocarbyl thiolate group) is independently an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or an aralkyl group; An alkyl group or an alkenyl group; Otherwise, an alkyl group; Otherwise, an alkenyl group; Otherwise, a cycloalkyl group; Otherwise, an aryl group; Or alternatively, an aralkyl group. Generally, alkyl, alkenyl, cycloalkyl, aryl, and aralkyl substituents have the same number of carbon atoms as the hydrocarbyl substituents described herein.

Linking substituent in the group I ligand, an alkyl group used in the linking group, or an alkyl group in the non-linking substituent in the I group ligand (such as a trihydrocarbylsilyl group, N, N - dihydrocarbylamine yl group, or hydrocarbyl thiolate group) is independently selected from the group consisting of a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec- Butyl group, a tert-butyl group, a n-pentyl group, a 2-pentyl group, a 3-pentyl group, A 2-butyl group, a neo-pentyl group, an n-hexyl group, an n-heptyl group, or an n-octyl group; Unless otherwise defined, the substituents may be the same or different and are selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec- Methyl-1-butyl group, tert-pentyl group, 3-methyl-1-butyl group, 3-methyl-2-butyl group or neo-pentyl group; Alternatively, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, or a neo-pentyl group; Otherwise, a methyl group; Otherwise, ethyl; An isopropyl group; Alternatively, a tert-butyl group; Otherwise, neo-pentyl group; Otherwise, n-hexyl; An n-heptyl group; Or alternatively an n-octyl group.

In certain embodiments described herein, both Group I ligands, Group II ligands, or Group I and Group II ligands are C ₂ to C ₂₀ alkenyl groups; Otherwise, a C ₃ to C ₁₅ alkenyl group; Otherwise, a C ₄ to C ₁₀ alkenyl group; Or alternatively may be substituted with a C ₄ to C ₈ alkenyl group. In any of the embodiments described herein, the substituents on the bridging bridge atom are selected from the group consisting of a C ₂ to C ₂₀ alkenyl group; Otherwise, a C ₃ to C ₁₅ alkenyl group; Otherwise, a C ₄ to C ₁₀ alkenyl group; Or alternatively a C ₄ to C ₈ alkenyl group. In certain of these optional embodiments and in one embodiment, the alkenyl groups have an omega (-) - position of the alkenyl moiety, i.e., "omega- Alkenyl "groups. ω- to alkenyl groups exemplified include, but are not limited to, formula _{-CH 2 (CH 2) n CH} = CH , and includes groups having _2, where n is 0 to 12; Otherwise, 1 to 9; Otherwise, 1 to 7; Otherwise, 1 to 6; Otherwise, 1 to 5; Alternatively 1 to 4; Otherwise, 1 to 3; Otherwise, it is an integer of 1 to 2. In another embodiment, and any embodiment, as an example of ω- alkenyl groups include, but are not limited to, formula _{-CH 2 (CH 2) m CH} = CH , and includes groups having _2, where m is 0; Unlike, 1, Unlike, 2, Unlike, 3, Unlike 4, Unlike, 5, Unlike, 6, Unlike, 7, Unlike, 8, Unlike, 9, Unlike, 10, Unlike, 11 or Unlike. In embodiments, any alkenyl substituent that may be used as the non-linking substituent in the Group I ligand, an alkenyl group that is used in the linking group, or an alkenyl group in the non-linking substituent in the I group ligand (such as, An N, N -dihydrocarbylamine group, or a hydrocarbyl thiolate group) includes an ethenyl group, a propenyl group, a butenyl group, a pentenyl group and a hexenyl group; A heptenyl group, or an octenyl group; A propenyl group, a butenyl group, a pentenyl group, a hexenyl group; Otherwise, an ethenyl group; Otherwise, a propenyl group; Otherwise, a butenyl group; Otherwise, a pentenyl group; Otherwise, a hexenyl group; Otherwise, a heptenyl group; Or alternatively an octenyl group.

In an embodiment, a non-linking substituent in the Group I ligand, a cycloalkyl group used in the linking group, or a cycloalkyl group in the non-linking substituent in the Group I ligand (such as a trihydrocarbylsilyl group, among others, N , N -dihydrocarbylamine yl group, or hydrocarbyl thiolate group) is a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, or a cyclohexyl group Tilyl group; A cyclopentyl group or a cyclohexyl group; Otherwise, a cyclopropyl group; Otherwise, a cyclobutyl group; Otherwise, a cyclopentyl group; Otherwise, a cyclohexyl group; Otherwise, a cycloheptyl group; Or alternatively it may be a cyclooctyl group. Linking substituent in the Group I ligand, an aryl group in the linking group, or an aryl group in the non-linking substituent in the Group I ligand (such as a trihydrocarbylsilyl group, among others, N, N -dihydrocarbylamine yl group, or hydrocarbyl thiolate group) is a phenyl group, a tolyl group, a xylyl group, or a 2,4,6-trimethylphenyl group; Otherwise, phenyl group; Otherwise, a tolyl group, otherwise, a xylyl group; Alternatively, it may be a 2,4,6-trimethylphenyl group. In an embodiment, a non-linking substituent in the Group I ligand, an aralkyl group used in the linking group, or an aralkyl group in the non-linking substituent in the Group I ligand (such as a trihydrocarbylsilyl group, among others, N , An N -dihydrocarbylamine yl group, or a hydrocarbyl thiolate group) may be a benzyl group.

In an embodiment, any hydrocarboxy substituent (s) that may be used as non-linking substituents in the Group I ligand is an alkoxy group, an aryl group, or an aralkoxy group; Otherwise, an alkoxy group; Otherwise, the Auroku period; Or alternatively, an aralkoxy group. Generally, alkoxy, aroxy, and aralkoxy substituents may have the same number of carbon atoms as the hydrocarboxy substituent group described herein. In an embodiment, any alkoxy substituent that may be used as a non-linking substituent in the Group I ligand is selected from the group consisting of a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, Butoxy group, tert-butoxy group, 3-methyl-1-butoxy group, 3-methyl-2 A butoxy group, or a neo-pentoxy group; Alternatively, a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group, or a neo-pentoxy group; Otherwise, a methoxy group; Otherwise, the ethoxy group; Alternatively isopropoxy; Otherwise, the tert-butoxy group; Or alternatively, a neo-pentoxy group. In an embodiment, any aryl substituent that may be used as the non-linking substituent in the Group I ligand is a phenoxy group, a tolyl group, a xylyl group, or a 2,4,6-trimethylphenoxy group; Otherwise, the phenoxy group; Otherwise, the tolyloide, unlike the xylock period; Alternatively, it may be a 2,4,6-trimethylphenoxy group. In an embodiment, any of the aryloxy substituents that may be used as non-linking substituents in the Group I ligand may be a benzyl group.

Throughout this disclosure, metallocenes are described as comprising at least one Group II ligand. In this embodiment and in certain embodiments, the Group II ligand is not a sigma-binding ligand and an η ⁵ -cycloalkadienyl-type ligand and is not a typical pi-binding η ^{x ≥ 5} ligand with respect to other metallocene compounds The pi-coupled ligands are included in the metallocene. In certain embodiments described herein, exemplary and alternative examples of Group II ligands include, but are not limited to, hydrides, halides, C ₁ -C ₃₀ η ^{x <5} - organic groups, C ₁ -C ₃₀ η ^{x < 5} -hydrocarbon group, a C ₁ -C ₃₀ aliphatic group, a C ₆ -C ₃₀ η ^{x <5} -aromatic group, a C ₂ -C ₃₀ η ^{x <5} -heterocyclic group, a C ₂ -C ₃₀ η ^{x <5} - hetero cycloalkyl _{^{group, C 4 -C 30 η x <}} 5 - hetero arene _{^{group, C 4 -C 30 η x <}} 5 - aryl heteroaryl _{^{group, C 1 -C 30 η x <}} 5 - organic heterocyclic group, C ₅ - C ₃₀ heteroaryl group are alkanes, C ₅ -C ₂₀ heteroaryl group are alkanes, C ₅ -C ₁₀ heteroaryl are alkanes, C ₁ -C ₃₀ sansogi, C ₁ -C ₃₀ Hwang, C ₀ -C ₃₀ group nitrogen, C ₀ Top -C _30, C ₀ -C ₃₀ group arsenic, C ₀ -C ₃₀ silicon group, C ₀ -C ₃₀ germanium group, C ₀ -C ₃₀ group tin, C ₀ -C ₃₀ delivery, C ₀ -C ₃₀ boron Or a C ₀ -C ₃₀ aluminum group; Alternatively, a hydride, _{^{halide, C 1 -C 20 η x <}} 5 - organic _{^{group, C 1 -C 20 η x <}} 5 - hydrocarbon group, C ₁ -C ₂₀ aliphatic _{^{groups, C 6 -C 20 η x <}} 5 aromatic _{^{groups, C 2 -C 20 η x <}} 5 - a heterocyclic _{^{group, C 2 -C 20 η x <}} 5 - bicyclo heteroaryl _{^{group, C 4 -C 20 η x <}} 5 - hetero arene group, C ₄ - C η ^x ₂₀ ^<5 - aryl heteroaryl _{^{group, C 1 -C 20 η x <}} 5 - organic heterocyclic group, C ₅ -C ₂₀ heteroaryl group are alkanes, C ₁ -C ₂₀ sansogi, C ₁ -C ₂₀ Hwang, C ₀ -C ₂₀ nitrogen group, C ₀ -C ₂₀ Top, C ₀ -C ₂₀ group arsenic, C ₀ -C ₂₀ silicon group, a germanium group C ₀ -C _20, C ₀ -C ₂₀ group tin, C ₀ -C delivery _20, C ₀ -C ₂₀ group of boron, aluminum, or C ₀ -C ₂₀ group; Alternatively, a hydride, _{^{halide, C 1 -C 10 η x <}} 5 - organic _{^{group, C 1 -C 10 η x <}} 5 - hydrocarbon group, C ₁ -C ₁₀ aliphatic _{^{groups, C 6 -C 10 η x <}} 5 C ₂ -C ₁₀ η ^{x <5} -heterocyclic group, C ₂ -C ₁₀ η ^{x <5} -cyclohetero group, C ₄ -C ₁₀ heteroareylene group, C ₄ -C ₁₀ η ^{x < 5-aryl} heteroaryl _{^{group, C 1 -C 10 η x <}} 5 - organic heterocyclic group, C ₅ -C ₁₀ heteroaryl are alkanes, C ₁ -C ₁₀ sansogi, C ₁ -C ₁₀ Hwang, C ₀ -C ₁₀ nitrogen group , C ₀ -C ₁₀ Top, C ₀ -C ₁₀ group arsenic, C ₀ -C ₁₀ silicon group, C ₀ -C ₁₀ germanium group, C ₀ -C ₁₀ group tin, C ₀ -C ₅ group tin, C ₀ delivery -C _10, C ₀ -C ₁₀ group of boron, aluminum, or C ₀ -C ₁₀ group; Alternatively, a hydride, halide, _{^{fluoride, C 1 -C 5 η x <}} 5 - organic ^{_{group, C 1 -C 5 η x <}} 5 - hydrocarbon group, C ₁ -C ₅ aliphatic groups, C ₆ -C ₁₀ η ^{x <5-aromatic _{group, C 6 -C 10 η x <}} 5 - arene group, C ₂ -C ₅ η ^{x <5,} - a heterocyclic group, C ₂ -C ₅ η ^{x <5,} - a cycloalkyl heterocyclic group, C ₄ -C ₅ heterocyclic arene _{^{group, C 4 -C 5 η x <}} 5 - aryl heteroaryl _{^{group, C 1 -C 5 η x <}} 5 - organic heterocyclic group, C ₅ -C ₁₀ heteroaryl are alkanes, C ₁ -C ₅ sansogi , C ₁ -C ₅ Hwang, C ₀ -C ₅ nitrogen group, C ₀ -C ₅ popular, C ₀ -C ₅ arsenic group, C ₀ -C ₅ silicon group, C ₀ -C ₅ germanium group, C ₀ - C ₅ comprises tin group, a C ₀ -C ₅ delivery, C ₀ -C ₅ boron group, an aluminum group, or C ₀ -C _5.

Alternatively, and in certain embodiments of the invention, each of the group II ligands are independently selected from halide, _{^{hydride, C 1 -C 30 η x <}} 5 - a hydrocarbyl group, C ₁ -C ₃₀ oxygen-coupler, C ₁ - C ₃₀ sulfur-coupler, C ₀ -C ₃₀ nitrogen-coupler, C ₀ -C ₃₀ a-coupler, C ₀ to C _{20 ^{non-small-coupler, C 1 -C 30 η x <}} 5 - Organic groups, C ₀ -C ₃₀ silicon-coupler, C ₀ -C _30, germanium-coupler, C ₀ -C ₃₀ tin-coupler, C ₀ to C ₃₀ of lead-coupler, C ₀ to C ₃₀ of boron-coupler, C ₀ to C ₃₀ aluminum-coupler, Or a C ₀ to C ₁₀ aluminum-linking group; Alternatively, a halide, a _{^{hydride, C 1 -C 20 η x <}} 5 - a hydrocarbyl group, C ₁ -C ₂₀ oxygen-coupler, C ₁ -C ₂₀ sulfur-coupler, C ₀ -C ₂₀ nitrogen-coupler, C ₀ -C ₂₀ a-coupler, C ₀ to C _{20 ^{non-small-coupler, C 1 -C 20 η x <}} 5 - Organic groups, C ₀ -C ₂₀ silicon-coupler, C ₀ -C ₂₀ germanium-coupler, C ₀ - A C ₂₀ tin-bond group, a C ₀ to C ₂₀ lead-bond group, or a C ₀ to C ₂₀ aluminum-bond group; Alternatively, a halide, a _{^{hydride, C 1 -C 10 η x <}} 5 - a hydrocarbyl group, C ₁ -C ₁₀ oxygen-coupler, C ₁ -C ₁₀ sulfur-coupler, C ₀ -C ₁₀ nitrogen-coupler, C ₀ -C ₁₀ a-coupler, C ₀ to C _{10 ^{non-small-coupler, C 1 -C 10 η x <}} 5 - Organic groups, C ₀ -C ₁₀ silicon-coupler, C ₀ -C ₁₀ germanium-coupler, C ₀ - A C ₀ to C ₁₀ tin-bond group, a C ₀ to C ₁₀ lead-bond group, a C ₀ to C ₁₀ boron-bond group, or a C ₀ to C ₁₀ aluminum- Or alternatively a halide, a hydride, a C ₁ -C ₅ η ^{x <5} -hydrocarbyl group, a C ₁ -C ₁₀ oxygen-linking group, a C ₁ -C ₁₀ sulfur-linking group, a C ₀ -C ₁₀ nitrogen- ₀ -C ₁₀ a-coupler, C ₀ to C _{6 ^{non-small-coupler, C 1 -C 5 η x <}} 5 - Organic groups, C ₀ -C ₁₀ silicon-coupler, C ₀ -C ₁₀ germanium-coupler, C ₀ A C ₀ to C ₁₀ tin-bond group, a C ₀ to C ₁₀ lead-bond group, a C ₀ to C ₁₀ boron-bond group, or a C ₀ to C ₁₀ aluminum-bond group.

In other embodiments described herein and in certain embodiments, any of the Group II ligands can be, but are not limited to, halides, hydrides, C ₁ -C ₂₀ η ^{x <5} -hydrocarbyl groups, C ₁ -C ₂₀ oxygen- A C ₁ -C ₂₀ sulfur-bonded group, a C ₀ -C ₃₀ nitrogen-bonded group, a C ₀ -C ₃₀ phosphorus-bonded group, a C ₁ -C ₂₀ η ^{x <5} -organyl group, a C ₀ -C ₃₀ silicon- , A C ₁ -C ₃₀ germanium-linking group, or a C ₁ -C ₃₀ tin-linking group; Alternatively, a halide, a ^{_{hydride, C 1 -C 10 η x <}} 5 - a hydrocarbyl group, C ₁ -C ₁₀ oxygen-coupler, C ₁ -C ₁₀ sulfur-coupler, C ₀ -C ₂₀ nitrogen-coupler, C ₀ A C ₁ -C ₂₀ phosphorus-linking group, a C ₁ -C ₁₀ η ^{x <5} -organyl group, a C ₀ -C ₃₀ silicon-bonding group, a C ₁ -C ₂₀ germanium-bonding group, or a C ₁ -C ₂₀ tin-bond group; Or alternatively, a halide, a ^{_{hydride, C 1 -C 5 η x <}} 5 - a hydrocarbyl group, C ₁ -C ₅ oxy-coupler, C ₁ -C ₅ sulfur-coupler, C ₀ -C ₁₀ nitrogen-coupler, C _A C ₀ -C ₁₀ phosphorus-containing group, a C ₁ -C ₅ η ^{x <5} -organyl group, a C ₀ -C ₁₀ silicon-bonding group, a C ₁ -C ₁₀ germanium-bonding group, or a C ₁ -C ₁₀ tin- do.

In yet another embodiment, and any embodiment disclosed herein, optionally each group II ligands are independently selected from halide, _{^{hydride, C 1 -C 20 η x <}} 5 - a hydrocarbyl group, C ₁ -C ₂₀ oxygen-coupler, C ₁ - C ₂₀ sulfur-coupler, C ₀ -C _{30 ^{nitrogen-coupler, C 1 -C 20 η x <}} 5 - Organic group, or C ₀ -C ₃₀ silicon-coupler; Alternatively, a halide, a _{^{hydride, C 1 -C 10 η x <}} 5 - a hydrocarbyl group, C ₁ -C ₁₀ oxygen-coupler, C ₁ -C ₁₀ sulfur-coupler, C ₀ -C ₂₀ nitrogen-coupler, C ₀ A C ₂ -C ₂₀ phosphorus-bonded group, a C ₁ -C ₁₀ η ^{x <5} -organyl group, or a C ₀ -C ₂₀ silicon-bonded group; Or alternatively, a halide, a _{^{hydride, C 1 -C 5 η x <}} 5 - a hydrocarbyl group, C ₁ -C ₅ oxy-coupler, C ₁ -C ₅ sulfur-coupler, C ₀ -C ₁₀ a-coupler, C ₁ -C ₅ η ^{x <5} -organyl group, or a C ₀ -C ₁₀ silicon-bonded group.

Alternatively, and in certain embodiments, each Group II ligand is independently selected from the group consisting of halides, hydrides, C ₁ to C ₂₀ hydrocarboxy groups (also referred to as hydrocarboxy groups), C ₁ to C ₂₀ heterocyclic groups, C ₆ to C ₂₀ η ¹ - aromatic groups, C ₁ to C ₂₀ η ¹ - a heteroaromatic group, C ₁ to C ₂₀ hydrocarbyl silyl group, C ₁ to C ₂₀ di-hydrocarbyl silyl group, C ₁ to C ₂₀ tree A C ₁ to C ₂₀ N -hydrocarbylamine group, a C ₁ to C ₂₀ N, an N -dihydrocarbylamine group, a C ₁ to C ₂₀ hydrocarbyl thiolate group, Or a C ₃ to C ₃₀ trihydrocarbylsiloxy group. In yet another alternative, and in each case, the Group II ligand is independently selected from the group consisting of halides, hydrides, C ₁ to C ₂₀ alkoxides, C ₆ to C ₂₀ aryloxides, C ₆ to C ₂₀ η ¹ -aromatic groups, , C ₁ to C ₂₀ N - alkyl, amido, C ₆ to C ₂₀ N - aryl amido group, C ₁ to C ₂₀ N, N - dialkyl amido, C ₇ to C ₂₀ N - alkyl - N - aryl amino A C ₁ to C ₂₀ alkyl thiolate, a C ₆ to C ₂₀ aryl thiolate, a C ₃ to C ₂₀ trialkylsiloxy, or a C ₁₈ to C ₃₀ triarylsiloxy.

In a further embodiment and in certain embodiments, each Group II ligand is independently selected from the group consisting of halides, C ₁ to C ₂₀ hydrocarbons (or hydrocarboxy groups), C ₁ to C ₃₀ hydrocarbyl, or C ₃ to C ₂₀ Trihydrocarbylsiloxy; Alternatively, a halide, a C ₁ to C ₁₀ hydrocarboxide, a C ₁ to C ₁₀ hydrocarbyl, or a C ₃ to C ₂₀ trihydrocarbylsiloxy; Alternatively, it may be a halide, a C ₁ to C ₅ hydrocarboxide, a C ₁ to C ₅ hydrocarbyl, or a C ₃ to C ₁₅ trihydrocarbylsiloxy. In another embodiment, and in certain embodiments, each Group II ligand is independently selected from the group consisting of halides, C ₁ to C ₂₀ hydrocarbons, or C ₁ to C ₃₀ hydrocarbyl; Alternatively, halide, C ₁ to C ₁₀ hydrocarbyl, or C ₁ to C ₁₀ hydrocarbyl; Or alternatively it may be a halide, a C ₁ to C ₅ hydrocarboxide, or a C ₁ to C ₅ hydrocarbyl. In another embodiment, and in certain embodiments, each Group II ligand is independently a halide or C ₁ to C ₂₀ hydrocarboxide; Alternatively, a halide or C ₁ to C ₁₀ hydrocarboxide; Or alternatively it may be halide or C ₁ to C ₅ hydrocarbyl. In another embodiment, each Group II ligand can be a halide.

Halides are described herein as halides that are used in potential non-linking substituents or linking groups in Group I ligands, and these halides can be used, non-limitingly and in any embodiment or example, as Group II ligands. Hydrocarbyl groups are described herein as hydrocarbyl groups in potential non-linking substituents or linking groups in group I ligands or hydrocarbyl groups in non-linking substituents in group I ligands, and these hydrocarbyl groups are non-limiting And in any embodiment or example, a Group II ligand. Hydrocarbyl groups are described herein as potential non-linking substituents in Group I ligands, and these hydrocarbyl groups can be used non-limitingly and in any embodiment or example, as Group II ligands.

The substituted amine yl group used in certain embodiments in which a substituted amide group is required may be an N -hydrocarbylamine dihalide or an N, N -dihydrocarbylamine dihalide. Hydrocarbyl groups are described herein, and these hydrocarbyl groups can be attached to the more-described N -hydrocarbylamine diaryl groups or N, N -dihydrocarbylamine diaryl groups that can be used in the various aspects and embodiments described herein And can be applied without limitation. In a non-limiting embodiment, N- hydrocarbyl amine N which group may be used in certain embodiments the required-hydrocarbyl amine group include, but are not limited to, N-methyl amine group (-NHCH _3), N - ethylamine group _{(-NHCH 2 CH 3), N} -n- propyl amine group _{(-NHCH 2 CH 2 CH 3)} , N - iso-propyl amine group _{(-NHCH (CH 3) 2)} , N -n- butyl amine group _{(-NHCH 2 CH 2 CH 2 CH} 3), N -t- butyl amine group _{(-NHC (CH 3) 3)} , n- n- pentylamine group _{(-NHCH 2 CH 2 CH 2 CH} 2 CH 3 ), N- neo-pentylamine group _{(-NHCH 2 C (CH 3)} 3), N- phenyl amine group (-NHC ₆ H _5), N- tolylamine group _{(-NHC 6 H 4 CH 3)} , or An N- xylyl amine di (-NHC ₆ H ₃ (CH ₃ ) ₂ ); Alternatively, an N- ethylamine di group; Otherwise, an N- propylamine di group; Or alternatively, an N- phenylamine yl group. N, N - di-hydrocarbyl amines which can be applied in any embodiment in which a journal is required to N, N - di-hydrocarbyl amine group include, but are not limited to N, N - dimethylamino group _{(-N (CH 3) 2)} , N, N - diethyl amine group _{(-N (CH 2 CH 3)} 2 ), N, N-di -n- propyl amine group _{(-N (CH 2 CH 2 CH} 3) 2), N, N - di-iso-propyl amine group _{(-N (CH (CH 3)} 2) 2 ), N, N - di -n- butyl amine group _{(-N (CH 2 CH 2 CH} 2 CH 3) 2), N, N - di -t- butyl-amine group _{(-N (C (CH 3)} 3 ) _2), N, N - di -n- pentyl amine group _{(-N (CH 2 CH 2 CH} 2 CH 2 CH 3) 2), N, N - di-neo-pentyl amine group (-N (CH _{2 C (CH 3) 3) 2} ), N, N- di-phenyl amine group _{(-N (C 6 H 5)} 2), N, N - di-tolyl amine group _{(-N (C 6 H 4 CH} 3 ) _2), or N, N- di-xylyl amine group _{(-N (C 6 H 3 (} CH 3) 2) 2); Alternatively, N, N -di- ethylamine di group; Alternatively, N, N-di- n-propylamine di group; Or alternatively, an N, N -di- phenylamine yl group. Halides that can be used in any embodiment requiring a halide substituent or group include fluorides, chlorides, bromides, or iodides; Otherwise, fluoride; Otherwise, chloride; Or alternatively, bromide. In some embodiments, substituents or groups that may be applied in embodiments requiring a substituent or group include halogenated hydrocarbyl groups. In an embodiment, the halogenated hydrocarbyl group may be a halogenated aromatic group or a halogenated alkyl group; Otherwise, a halogenated aromatic group; Or alternatively, a halogenated alkyl group. A commonly used halogenated aromatic group is pentafluorophenyl. The halogenated alkyl group which is most frequently used is trifluoromethyl.

Exemplary aromatic groups include, in each case, including, but not limited to, phenyl, naphthyl, anthracenyl, and the like, and substituted derivatives thereof. In some embodiments, the aromatic group may be substituted phenyl groups. The substituted phenyl group may be substituted at the 2 position, 3 position, 4 position, 2 and 4 position, 2 and 6 position, 2 and 5 position, 3 and 5 position, or 2, 4, and 6 position; Unlike the 2 position, 4 position, 2 and 4 position, 2 and 6 position, or 2, 4, and 6 positions; Otherwise, 2 positions; Otherwise, 3 positions; Otherwise, 4 positions; Otherwise, positions 2 and 4; Otherwise, positions 2 and 6; Otherwise, positions 3 and 5; Or alternatively at the 2, 4, and 6 positions. The likely substituents are halide, an alkyl group, an alkoxy group, an amine group, N- hydrocarbyl amine day, and / or N, N - di-hydrocarbyl amine group; Alternatively, a halide, an alkyl group, or an alkoxy group; Otherwise, a halide or alkyl group; Otherwise, a halide or alkoxy group; Otherwise, halide; Otherwise, an alkyl group; Or alternatively, an alkoxy group. Halides, alkyl groups, and alkoxy groups are independently described herein and may be used as each independent substituent, but not in a limited manner. In some non-limiting embodiments, substituted aromatic groups include, but are not limited to, tolyl (2-, 3-, 4-, or mixtures thereof), xylyl (2,3-, 2,4-, 2,5 -, 3,4-, 3,5-, 2,6-, or mixtures thereof), mesityl, pentafluorophenyl, C ₆ H ₄ OMe (2-, 3-, 4-, C ₆ H ₄ NH ₂ (2-, 3-, 4-, or mixtures thereof), C ₆ H ₄ NMe ₂ (2-, 3-, 4- or mixtures thereof), C ₆ H ₄ CF ₃ -, 3-, 4-, or mixtures _{thereof), C 6 H 4 F,} C 6 H 4 Cl (2-, 3-, 4-, or mixtures _{thereof), C 6 H 3 (OMe} ) 2 (2, 3-, 2,4-, 2,5-, 3,4-, 3,5-, 2,6- or mixtures thereof), C ₆ H ₃ (CF ₃ ) ₂ (2,3- 4, 2,5-, 3,4-, 3,5-, 2,6-, or mixtures thereof), and the like, and includes any of these heteroatom substituted analogs as described in the Definitions section . Other substituted aromatic groups, and combinations of substituted aromatic groups, can be considered in the present invention.

Examples of heterocyclic compounds from which heterocyclic enantiomers are derived include, but are not limited to, aziridine, azirine, oxirane (ethylene oxide), oxylene, thiiran (ethylene sulfide), dioxirane, azetidine, oxetane , Thiazole, dioxetane, dithiethane, tetrahydropyrrole, pyrrole, tetrahydrofuran, furan, tetrahydrothiophene, thiophene, imidazolidine, pyrazole, imidazole, oxazolidine, oxazole, isoxazole , Thiazolidine, thiazole, isothiazole, dioxolane, dithiolane, triazole, dithiazole, tetrazole, piperidine, pyridine, tetrahydropyran, pyran, Oxazine, thiazine, dithiane, dioxane, dioxin, triazine, trioxane, tetrazine, azepine, thiepine, diazepine, morpholine, quinoline, 1,2-thiazole, bicyclo [3.3. 1] tetrasiloxane, and substituted analogs thereof. Accordingly, the present invention relates to a heterocyclic compound having at least one hetero ring selected from the group consisting of a heterocyclyl group, a heterocyclylene group, a heterocyclic group, a cycloheteryl group, a cycloheterylene group, a cycloheteroaryl group, a heteroaryl group, a heteroarylene group, An arylheterylene group, an arylhetero group, an organoheteryl group, an organic heteroarylene group, or an organic hetero group may be derived from these and similar heterocyclic compounds and substituted analogues. Additional explanation is provided in the definition section.

In another embodiment, and in any of the embodiments described herein wherein the ligand is selected to confer optical activity on the metallocene, the metallocene is in racemic form. Alternatively, and in certain embodiments where the ligand is selected to impart optical activity to the metallocene, the metallocene is in a non-racemic form. In addition, and in certain embodiments where the ligand is selected to impart optical activity to the metallocene, the metallocene may be substantially optically pure (greater than 99.5% of the enantiomeric excess), or optically not pure have. Thus, any enantiomers, diastereomers, epimers, epimers, and the like of the metallocenes used in the methods described herein may be included in the present invention.

In other embodiments and in any of the embodiments described herein, the metallocene is represented by the formula (? ⁵ -cycloalkadienyl) M ³ R ⁹ _n X ⁹ _3-n ; Alternatively, it may have the formula (? ⁵ -cycloalkadienyl) ₂ M ³ X ⁹ ₂ . In an embodiment, M ³ is any metallocene metal as described herein, each η ⁵ -cycloalkadienyl ligand is independently any η ⁵ -cycloalkadienyl ligand described herein, each R ⁹ is independently , Each X ⁹ may independently be any halide, hydrocarbyl group, hydrocarboxy group described herein, and n may be an integer from 1 to 3. The term &quot; hydrocarbyl group &quot; In some non-limiting embodiments, M ³ is Ti, Zr, or Hf, each η ⁵ -cycloalkadienyl ligand is a substituted or non-substituted cyclopentadienyl ligand, a substituted or non- Or a substituted or unsubstituted fluorenyl ligand, each R ⁹ is independently a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ cycloalkyl group, a C _A C ₆ -C ₂₀ aryl group, or a C ₇ -C ₂₀ aralkyl group, each X ⁹ is independently a halide, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C Substituted or unsubstituted C ₁ -C ₂₀ alkoxy, substituted or unsubstituted C ₆ -C ₂₀ aryl, substituted or unsubstituted C ₇ -C ₂₀ aralkyl, substituted or unsubstituted C ₁ -C ₂₀ alkoxy Or a substituted or non-substituted C ₆ -C ₂₀ aryloxydic group, and n may be an integer of 1 to 3. When metallocenes have the formula (η ⁵ -cycloalkadienyl) ₂ M ³ X ⁹ ₂ , the two (η ⁵ -cycloalkadienyl) ligands can be joined by any of the linkages described herein. When metallocenes have the formula (? ⁵ -cycloalkadienyl) M ³ R ⁹ _n X ⁹ _{3 -n} or the formula (? ⁵ -cycloalkadienyl) ₂ M ³ X ⁹ ₂ , the η ⁵ -cycloalkane Any non-linking substituent at dien, R ⁹ , and / or X ⁹ may be independently any of the substituents described herein. In some embodiments, when the metallocene has formula (? ⁵ -cycloalkadienyl) M ³ R ⁹ _n X ⁹ _{3 -n} or formula (? ⁵ -cycloalkadienyl) ₂ M ³ X ⁹ ₂ , η ⁵ - cyclo alkynyl diene yl, R ^9, and / or any ratio in X ⁹ - connection substituents are independently selected from halide, C ₁ to C ₂₀ alkoxy deugi, C ₆ to C ₂₀ aryl hydroxide group, C ₆ to about C ₂₀ aromatic group, an amido group, C ₁ to C ₂₀ N - alkyl, amido, C ₆ to C ₂₀ N - aryl amido group, C ₁ to C ₄₀ N, N - dialkyl amido, C ₇ to C ₄₀ N -alkyl- N -arylamido groups, C ₁ to C ₂₀ alkylthioate groups, C ₆ to C ₂₀ arylthioate groups, C ₃ to C ₂₀ trialkylsiloxy groups, or C ₁₈ to C ₄₅ triarylsiloxy groups Lt; / RTI &gt;

A wide variety of metallocenes can be used in the catalyst systems described herein and / or the processes disclosed herein. In one embodiment and in any of the embodiments described herein, the metallocene is represented by the formula:

,

,

,

, 또는 이들의 임의 조합을 가질 수 있다. 일 양태에서 및 본원에 기재된 임의 실시예에서, 메탈로센은 식:

,

,

,

, Or any combination thereof. In one embodiment and in any of the embodiments described herein, the metallocene is represented by the formula:

,

,

,

, 또는 이들의 임의 조합을 가질 수 있다. 이들 양태에서, E는 본원에 기재된 임의의 가교 원자일 수 있고, 및 R1, R2, 및 R3은, 각각의 경우에 독립적으로 본원에 기재된 임의의 히드로카르빌기일 수 있다. 일부 비-제한적 실시예들에서, E는 C, Si, Ge, 또는Sn일 수 있고, 및 각각의 경우에, R1, R2, 및 R3는 독립적으로 H 또는 본원에 기재된 임의의 C₁-C₂₀ 히드로카르빌기일 수 있다.

,

,

,

, Or any combination thereof. In these embodiments, E may be any of the bridging atoms described herein, and R1, R2, and R3 may in each case independently be any hydrocarbyl group described herein. Some non-limiting examples of, E is C, Si, Ge, or may be Sn, and in each case, R1, R2, and R3 are any of C ₁ -C ₂₀ described herein independently H or Hydrocarbyl group.

In other non-limiting embodiments and in any of the embodiments described herein, the metallocene may have the formula:

.

.

In this embodiment, E is any bridging atom, R ^A described herein may be any hydrocarbyl group, R ^B according to H or herein is any of alkenyl groups described herein, R ³ is any of the hydrochloride according to H or present And R &lt; ⁴ &gt; may be H or any hydrocarbyl group described herein. In some non-limiting embodiments, E is C, Si, Ge, or Sn, R ^A is H or a C ₁ -C ₂₀ hydrocarbyl group, R ^B is a C ₃ -C ₁₂ alkenyl group, R ³ is H or C ₁ -C ₁₅ hydrocarbyl group, and R ⁴ may be H or a C ₁ -C ₂₀ hydrocarbyl group.

In another embodiment and in any of the embodiments described herein, the metallocene may comprise, consist essentially of, or consist of the following alone or in any combination:

,

,

,

,

,

,

,

,

,

,

,

,

,

,

, 또는

.

,

,

,

,

,

,

,

,

,

,

,

,

,

,

, or

.

In other embodiments and in any of the embodiments described herein, the metallocene may comprise, consist essentially of, or consist of the following alone or in any combination:

,

,

,

,

,

,

,

,

,

,

,

,

,

, 또는

.

,

,

,

,

,

,

,

,

,

,

,

,

,

, or

.

In further embodiments and in certain embodiments of the invention, the metallocene may comprise, consist essentially of, or consist of the following alone or in any combination:

,

,

,

,

,

,

,

,

,

,

,

,

,

, 또는

.

,

,

,

,

,

,

,

,

,

,

,

,

,

, or

.

In additional embodiments and in any of the embodiments described herein, the metallocene may comprise, consist essentially of, or consist of the following alone or in any combination:

,

,

, 또는

.

,

,

, or

.

,

,

,

, 또는 이들의 조합; 달리,

,

,

, 또는 이들의 조합; 달리,

; 달리,

; 달리,

; 또는 달리,

을 포함하거나, 실질적으로 이루어지거나, 또는 이루어질 수 있다. 또 다른 양태에 의하면 및 임의 실시예에서 본원에 기재된, 메탈로센은: In other embodiments and in any of the embodiments described herein, the metallocene is:

,

,

,

, Or a combination thereof; Otherwise,

,

,

, Or a combination thereof; Otherwise,

; Otherwise,

; Otherwise,

; Alternatively,

Or may be made substantially, or may be made. According to another embodiment, and in certain embodiments, the metallocenes described herein are:

,

,

,

, 또는 이들의 임의의 조합; 달리,

,

,

, 또는 이들의 임의 조합; 달리,

; 달리,

; 달리,

; 또는 달리,

을 포함하거나, 실질적으로 이루어지거나, 또는 이루어진다. 이들 양태에서, 각각의 R²⁰, R²¹, R²³, 및 R²⁴ 은 독립적으로 수소 또는 본원에 기재된 임의의 히드로카르빌기, 및 각각의 X¹², X¹³, X¹⁵, 및 X¹⁶ 은 독립적으로 본원에 기재된 임의의 할라이드일 수 있다. 일부 실시예들에서, 각각의 R²⁰, R²¹, R²³, 및 R²⁴ 은 독립적으로 수소, C₁ 내지 C₂₀ 알킬기, 또는 C₁ 내지 C₂₀ 알케닐기, 및 각각의 X¹², X¹³, X¹⁵, 및 X¹⁶ 는 독립적으로 F, Cl, Br, 또는 I일 수 있다. 다른 실시예에서, 각각의 R²⁰, R²¹, 및 R²³ 은 독립적으로 수소, C₁ 내지 C₁₀ 알킬기, 또는 C₁ 내지 C₁₀ 알케닐기일 수 있고, 및 각각의 X¹², X¹³, 및 X¹⁵ 는 독립적으로 Cl 또는 Br일 수 있다.

,

,

,

, Or any combination thereof; Otherwise,

,

,

, Or any combination thereof; Otherwise,

; Otherwise,

; Otherwise,

; Alternatively,

Or substantially consists of, or consists of, the. In these embodiments, each of R ²⁰ , R ²¹ , R ²³ , and R ²⁴ is independently hydrogen or any hydrocarbyl group described herein, and each of X ¹² , X ¹³ , X ¹⁵ , and X ¹⁶ is independently Lt; / RTI &gt; can be any halide described herein. In some embodiments, each of R ^20, R ^21, R ^23, and R ²⁴ are independently hydrogen, C ₁ to C ₂₀ alkyl group, or a C ₁ to C ₂₀ alkenyl group, and each of X ^12, X ^13, X ¹⁵ , and X ¹⁶ may independently be F, Cl, Br, or I. In another embodiment, each R ²⁰ , R ²¹ , and R ²³ may independently be hydrogen, a C ₁ to C ₁₀ alkyl group, or a C ₁ to C ₁₀ alkenyl group, and each of X ¹² , X ¹³ , and X ¹⁵ can be independently Cl or Br.

According to another embodiment and in certain embodiments described herein, the metallocene is selected from the group consisting of:

,

,

,

,

,

,

, ,

,

,

,

,

,

,

,

,

, ,

,

,

Or any combination thereof; Otherwise,

,

,

,

,

,

,

,

,

Or any combination thereof; Otherwise,

,

,

, 또는 이들의 임의 조합; 달리,

; 달리,

; 달리,

; 달리,

; 달리,

; 달리,

; 달리,

; 달리,

; 또는 달리,

을 포함하거나, 실질적으로 이루어지거나, 또는 이루어진다.

,

,

, Or any combination thereof; Otherwise,

; Otherwise,

; Otherwise,

; Otherwise,

; Otherwise,

; Otherwise,

; Otherwise,

; Otherwise,

; Alternatively,

Or substantially consists of, or consists of, the.

In other embodiments and in any of the embodiments described herein, the metallocene is:

을 포함하거나, 실질적으로 이루어지거나, 또는 이루어진다.

Or substantially consists of, or consists of, the.

In an embodiment, each R ²⁰ may independently be hydrogen, a C ₁ to C ₁₀ alkyl group, or a C ₁ to C ₁₀ alkenyl group, and each X ¹² may independently be Cl or Br. In another embodiment, each R ²⁰ can independently be a C ₁ to C ₁₀ alkyl group and each X ¹² can independently be Cl or Br. In a non-limiting embodiment, the metallocene is:

,

,

, 또는 이들의 임의 조합; 달리,

,

, 또는 이들의 임의 조합을 포함하거나, 실질적으로 이루어지거나, 또는 이루어진다.

,

,

, Or any combination thereof; Otherwise,

,

, &Lt; / RTI &gt; or any combination thereof.

In another embodiment and in the embodiments described herein, the metallocene is:

을 포함하거나, 실질적으로 이루어지거나, 또는 이루어진다.

Or substantially consists of, or consists of, the.

In some non-limiting embodiments, each of R ²³ and R ²⁴ can independently be hydrogen, a C ₁ to C ₁₀ alkyl group, or a C ₁ to C ₁₀ alkenyl group, and each X ¹⁵ is independently Cl or Br. &Lt; / RTI &gt; In other non-limiting embodiments, each of R ²³ and R ²⁴ can independently be a C ₁ to C ₁₀ alkyl group or a C ₁ to C ₁₀ alkenyl group, and each X ¹⁵ can independently be Cl or Br have. In another non-limiting embodiment, the metallocene is:

을 포함하거나, 실질적으로 이루어지거나, 또는 이루어진다.

Or substantially consists of, or consists of, the.

In another embodiment and in any of the embodiments described herein, the metallocene is selected from the group consisting of:

을 포함하거나, 실질적으로 이루어지거나, 또는 이루어진다.

Or substantially consists of, or consists of, the.

In some non-limiting embodiments, each R ²⁵ can independently be hydrogen, a C ₁ to C ₁₀ alkyl group, or a C ₁ to C ₁₀ alkenyl group, and each X ²⁰ can independently be Cl or Br have. In other non-limiting embodiments, each R ²⁵ may independently be a C ₁ to C ₁₀ alkyl group or a C ₁ to C ₁₀ alkenyl group, and each X ²⁰ may independently be Cl or Br. In still other non-limiting embodiments, each R ²⁵ can independently be a C ₁ to C ₁₀ alkyl group, and each X ²⁰ can independently be Cl or Br. In another non-limiting embodiment, the metallocene is:

,

,

, 또는 이들의 조합; 달리,

,

,

, 또는 이들의 조합; 달리,

; 달리,

; 달리,

; 또는 달리,

을 포함하거나, 실질적으로 이루어지거나, 또는 이루어진다. ,

,

,

, Or a combination thereof; Otherwise,

,

,

, Or a combination thereof; Otherwise,

; Otherwise,

; Otherwise,

; Alternatively,

Or substantially consists of, or consists of, the.

In other embodiments and in any of the embodiments described herein, the metallocene comprises, consists essentially of, or consists of the following and any combination thereof:

Bis (cyclopentadienyl) hafnium dichloride,

Bis (cyclopentadienyl) zirconium dichloride,

1,2-ethanediyl bis (? ⁵ -1-indenyl) di-n-butoxy hafnium,

1,2-ethanediylbis (? ⁵ -1-indenyl) dimethylzirconium,

3,3-pentane diyl bis (η ⁵ -4,5,6,7- tetrahydro-1-indenyl) hafnium chloride 2,

Phenyl silyl bis (η ⁵ -4,5,6,7- tetrahydro-1-indenyl) zirconium chloride 2,

Bis (n-butylcyclopentadienyl) di-t-butylamido hafnium,

Bis (n-butylcyclopentadienyl) zirconium dichloride,

Bis (ethylcyclopentadienyl) zirconium dichloride,

Bis (propylcyclopentadienyl) zirconium dichloride,

Dimethylsilylbis (1-indenyl) zirconium dichloride,

Nonyl (phenyl) silylbis (1-indenyl) hafnium dichloride,

Dimethylsilylbis (? ⁵ -4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride,

Dimethylsilylbis (2-methyl-1-indenyl) zirconium dichloride,

Ethane diyl bis (9-fluorenyl) zirconium dichloride,

Indenyl diethoxy titanium (IV) chloride,

(Isopropylamido-dimethylsilyl) cyclopentadienyl titanium dichloride,

Bis (pentamethylcyclopentadienyl) zirconium dichloride,

Bis (indenyl) zirconium dichloride,

Methyl octylsilylbis (9-fluorenyl) zirconium dichloride,

Bis [1- ( N, N -diisopropylamino) borate benzene] hydrido zirconium trifluoromethylsulfonate,

Bis (cyclopentadienyl) hafnium dimethyl,

Bis (cyclopentadienyl) zirconium dibenzyl,

1,2-ethanediylbis (? ⁵ -1-indenyl) dimethyl hafnium,

1,2-ethanediylbis (? ⁵ -1-indenyl) dimethylzirconium,

3,3-pentane diyl bis (η ⁵ -4,5,6,7- tetrahydro -l- indenyl) hafnium dimethyl,

Methylphenylsilylbis (? ⁵ -4,5,6,7-tetrahydro-1-indenyl) zirconium dimethyl,

Bis (1- n -butyl-3-methyl-cyclopentadienyl) zirconium dimethyl,

Bis ( n -butylcyclopentadienyl) zirconium dimethyl,

Dimethylsilylbis (1-indenyl) zirconium bis (trimethylsilylmethyl),

Octyl (phenyl) silylbis (1-indenyl) hafnium dimethyl,

Dimethylsilylbis (? ⁵ -4,5,6,7-tetrahydro-1-indenyl) zirconium dimethyl,

Dimethylsilylbis (2-methyl-1-indenyl) zirconium dibenzyl,

1,2-ethanediylbis (9-fluorenyl) zirconium dimethyl,

(Indenyl) trisbenzyl titanium (IV),

(Isopropylamido dimethylsilyl) cyclopentadienyl titanium dibenzyl,

Bis (pentamethylcyclopentadienyl) zirconium dimethyl,

Bis (indenyl) zirconium dimethyl,

Methyl (octyl) silylbis (9-fluorenyl) zirconium dimethyl,

Bis (2,7-di- tert -butylfluorenyl) -ethane-1,2-diyl) zirconium (IV)

(Η ⁵ -cyclopentadienyl) -2- (η ⁵ -fluoren-9-yl) hex-5-enzirconium (IV)

(侶⁵ -cyclopentadienyl) -2- (侶⁵ -2,7-di- tert- butylfluoren-9-yl) hex-5- enzirconium (IV)

(Η ⁵ -cyclopentadienyl) -2- (η ⁵ -fluoren-9-yl) hept-6-enzirconium (IV)

(侶⁵ -cyclopentadienyl) -2- (侶⁵ -2,7-di- tert- butylfluoren-9-yl) hept-6-enzirconium (IV)

Enzirconium (IV) 2 chloride, 2-chloropentadienyl, 1- (η ⁵ -cyclopentadienyl) -1- (η ⁵ -fluoren-9-

(Η ⁵ -cyclopentadienyl) -1- (η ⁵ -2,7-di- tert- butylfluoren-9-yl) -1-phenylpent-4-enzirconium (IV)

(Η ⁵ -cyclopentadienyl) -1- (η ⁵ -fluoren-9-yl) -1-phenylhex-5-enzirconium (IV)

1- (η ⁵ -cyclopentadienyl) -1- (η ⁵ -2,7-di- tert- butylfluoren-9-yl) -1-phenylhex-5-enzirconium (IV) 2 chloride.

In other embodiments and in any of the embodiments described herein, the metallocene is selected from the group consisting of rac -C ₂ H ₄ (η ⁵ -indene) ₂ ZrCl ₂ , rac -Me ₂ Si (η ⁵ -indene) ₂ ZrCl ₂ , Me (octyl) Si (η ⁵ - _{fluorenyl) 2 ZrCl 2, rac -Me 2} Si (η 5 -2-Me-4-Ph- _{-indenyl) 2 ZrCl 2, rac -C 2} H 4 (η 5 - 2-Me-indenyl) ₂ ZrCl ₂ , Me (Ph) Si (η ⁵ -fluorenyl) ₂ ZrCl ₂ , rac -Me ₂ Si (η ⁵ -3-n-Pr-cyclopentadienyl) ₂ ZrCl ₂ , Me ₂ Si (η ⁵ -Me ₄ -cyclopentadienyl) ₂ ZrCl ₂ , or Me ₂ Si (η ⁵ -cyclopentadienyl) ₂ ZrCl ₂ alone or in any combination, , Or.

In other embodiments and in any of the embodiments described herein, the metallocene includes two η ⁵ -cyclopentadienyl-type ligands linked by a link consisting of one, two, or three bridging atoms. In other embodiments and in any of the embodiments described herein, the metallocene is a linking group consisting of one, two, or three bridging atoms and is not another ligand in the metallocene, i.e., an? ⁵ -cyclopentadienyl-type ligand a η ⁵ coupled to ligand-cyclopentadienyl-type ligands include. Each of these bridges can be further substituted if necessary. Fully substituted bridging or bridging atoms are referred to as "linking groups " with these substituents which are not cyclopentadienyl-type ligand substituents. By way of this naming example, potential linkers include -CH ₂ CH ₂ - or -CH (CH ₃ ) CH (CH ₃ ) -, all of which include C ₂ bridges. Thus, the -CH ₂ CH ₂ -connector is generally described as a non-substituted linker and the linker -CH (CH ₃ ) CH (CH ₃ ) - is generally described as a substituted linker.

The chemically-treated solid oxide

One aspect of the present invention provides an oligomerization process (or PAO process, which comprises contacting a catalytic system comprising an alpha olefin monomer and a metallocene). In an embodiment, the catalyst system may further comprise an activator. In one aspect, the present invention encompasses a catalyst system comprising at least one metallocene and at least one activator. An exemplary activating agent is a chemically-treated solid oxide. The term "chemically-treated solid oxide" is used interchangeably with similar terms such as "solid oxide treated with an electron-attracting anion," " treated solid oxide, " It is used interchangeably. While not intending to be bound by theory, it is believed that the chemically-treated solid oxide functions as an acidic activator-support. In one embodiment and in certain embodiments, the chemically-treated solid oxide may be used in combination with an organoaluminum compound or a similar active aid or alkylating agent. In one aspect and in some embodiments, the chemically-treated solid oxide may be used in combination with an organoaluminum compound. In other embodiments and in certain embodiments, the metallocene may be "pre-activated" prior to being used in the catalyst system to be alkylated. In one embodiment and in certain embodiments, the chemically-treated solid oxide can only be used as an activator. In yet another embodiment and in certain embodiments, the metallocene is "pre-activated" and the chemically-treated solid oxide is another activator; Or alternatively, in combination with multiple other activators.

In an embodiment and in certain embodiments of the present invention, the catalyst system comprises at least one chemically-treated solid oxide comprising at least one solid oxide treated with at least one electron-attracting anion, Surface area, and the electron-attracting anion includes any anion that increases the acidity relative to the solid oxide not treated with at least one electron-attracting anion.

In another aspect and in certain embodiments of the present invention, the catalyst system comprises a chemically-treated solid oxide comprising a solid oxide treated with an electron-attracting anion, wherein:

The solid oxide is selected from silica, alumina, silica-alumina, aluminum phosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or mixtures thereof; And

Electron-attracting anions are selected from fluorides, chlorides, bromides, phosphates, triflates, bisulfates, sulfates, fluorophosphates, fluorosulfates, or any combination thereof.

In another aspect and in certain embodiments of the present invention, the catalyst system comprises a chemically-treated solid oxide comprising a solid oxide treated with an electron-attracting anion, wherein:

The solid oxide is selected from silica, alumina, silica-alumina, titania, zirconia, mixed oxides thereof, or mixtures thereof; And

The electron-attracting anion is selected from fluorides, chlorides, bisulfates, sulfates, or any combination thereof.

In other embodiments and in certain embodiments of the invention, the chemically-treated solid oxide is selected from the group consisting of fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, Alumina, fluorinated silica-zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, or any combination thereof; Alternatively, fluorinated alumina, chlorinated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, sulfated silica-zirconia, or any combination thereof; Otherwise, fluorinated alumina; Otherwise, chlorinated alumina; Alternatively, alumina bromide; Otherwise, sulfated alumina; Alternatively, fluorinated silica-alumina; Alternatively, chlorinated silica-alumina; Alternatively, brominated silica-alumina; Alternatively, sulfated silica-alumina; Alternatively, fluorinated silica-zirconia; Alternatively, chlorinated silica-zirconia; Alternatively, brominated silica-zirconia; Alternatively, it may be a sulfurized silica-zirconia. In addition, and in another aspect, the chemically-treated solid oxide is selected from the group consisting of zinc, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum, or any combination thereof; Alternatively, zinc, nickel, vanadium, a stock, or any combination thereof; Otherwise, zinc; Otherwise, nickel; Otherwise, vanadium; Otherwise, silver; Otherwise, copper; Otherwise, gallium; Otherwise, annotation; Otherwise, tungsten; Or alternatively a metal or metal ion selected from molybdenum.

In another embodiment and in certain embodiments of the invention, the chemically-treated solid oxide may comprise at least one solid oxide compound and at least one contact product of an electron-attracting anion source. The solid oxide compound and the electron-attracting anion source are independently described herein and may be any combination of at least one solid oxide compound and at least one electron-draw anion source to further describe the chemically-treated solid oxide comprising the contact product Lt; / RTI &gt; That is, the chemically-treated solid oxide is provided by contacting or treating the solid oxide with an electron-attracting anion source. The solid oxide compound and the electron-attracting anion source are independently described herein and may be any combination of at least one solid oxide compound and at least one electron-draw anion source to further describe the chemically-treated solid oxide comprising the contact product Lt; / RTI &gt; In one embodiment, the solid oxide compound comprises, substantially consists of, or consists of an inorganic oxide. The solid oxide compound need not be calcined before contacting the electron-attracting anion source. The contact product solid oxide compound may be sintered during or after contact with the electron-attracting anion source. In this embodiment, the solid oxide compound is calcined or non-calcined; Otherwise, firing; Or otherwise, can be non-calcined. In another embodiment, the activator-support comprises at least one calcined solid oxide compound and at least one contact product of an electron-attracting anion source.

Although not intending to be bound by theory, the chemically-treated solid oxide, also referred to as the activator-support, exhibits a higher acidity than the corresponding non-treated solid oxide compound. The chemically-treated solid oxide functions as a catalyst activator to the corresponding non-treated solid oxide compound. The chemically-treated solid oxide may activate the metallocene without additional activators, but additional activators may be used in the catalyst system. For example, it may be useful to include an organoaluminum compound in the catalyst system with metallocene and chemically-treated solid oxides. The activated function of the activator-support for improved activity throughout the catalyst system is evident relative to the corresponding non-treated solid oxide.

In one aspect, the chemically-treated solid oxide of the present invention is a combination of a solid inorganic oxide material, a mixed oxide material, or an inorganic oxide material that is chemically-treated with an electron-attracting component and optionally treated with a metal; A solid inorganic oxide material that is otherwise chemically-treated with an electron-attracting component and optionally treated with a metal; Alternatively, a mixed oxide material chemically-treated with an electron-attracting component and optionally treated with a metal; Or otherwise, i.e., chemically-treated with an electron-attracting component, and optionally a metal-treated inorganic oxide material. Thus, the solid oxides of the present invention encompass oxide materials (such as alumina), "mixed oxide" compounds (such as silica-alumina), and combinations and mixtures thereof. The mixed oxide compound (e.g., silica-alumina) can be single or multiple chemical having one or more metals bonded with oxygen to form a solid oxide compound, and is included in the present invention. The solid inorganic oxide material, mixed oxide material, inorganic oxide material combination, electron-attracting component, and optional metal may be applied in any combination to further describe the chemically-treated solid oxide independently described herein.

In one aspect of the present invention and in certain embodiments, the chemically-treated solid oxide may further comprise a metal or metal ion. In an embodiment, the metal of the metal or metal ion is selected from the group consisting of zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, or any combination thereof; Alternatively, zinc, nickel, vanadium, titanium, or tin, or any combination thereof; Alternatively, it may comprise, consist essentially of, or consist of zinc, nickel, vanadium, tin, or any combination thereof. In some embodiments, the metal of the metal or metal ion is zinc; Otherwise, nickel; Otherwise, vanadium; Otherwise, titanium; Otherwise, silver; Otherwise, copper; Otherwise, gallium; Otherwise, annotation; Otherwise, tungsten; Or alternatively, may comprise, consist essentially of, or consist of molybdenum.

In certain embodiments and in certain embodiments, a chemically-treated solid oxide further comprising a metal or metal ion, including but not limited to zinc-impregnated chlorinated alumina, titanium-impregnated fluorinated alumina, zinc-impregnated fluorinated alumina, zinc- Impregnated silica-alumina, zinc-impregnated fluorinated silica-alumina, zinc-impregnated sulfated alumina, chlorinated zinc aluminate, fluorinated zinc aluminate, zinc sulfated aluminate, or any combination thereof and; Alternatively, the chemically-treated solid oxide may be selected from the group consisting of fluorinated alumina, chlorinated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, Lt; / RTI &gt; In some embodiments, the chemically-treated solid oxide further comprising a metal or metal ion is zinc-impregnated chlorinated alumina; Alternatively, titanium-impregnated fluorinated alumina; Alternatively, zinc-impregnated fluorinated alumina; Alternatively, zinc-impregnated chlorinated silica-alumina; Alternatively, zinc-impregnated fluorinated silica-alumina; Alternatively, zinc-impregnated sulfated alumina; Otherwise, chlorinated zinc aluminate; Otherwise, fluorinated zinc aluminate; Alternatively, or alternatively, it may comprise, consist essentially of, or consist of zinc sulphate aluminate.

In other embodiments and in certain embodiments, the chemically-treated solid oxide of the present invention comprises a relatively high-pore solid oxide exhibiting Lewis acid or Bronsted acid behavior. The solid oxide is treated with an electron-attracting component, typically an electron-attracting anion to form an activator-support. Although not intending to be bound by the following statements, it is believed that treating the inorganic oxide with an electron-attracting component increases or enhances the acidity of the oxide. Thus, in one embodiment, the activator-support typically exhibits a greater Lewis or Bronsted acidity than the untreated solid oxide, or the activator-support has a greater number of acid sites than the untreated solid oxide, I have. One way to quantify the acidity of chemically treated solid oxide materials and untreated solid oxide materials is to compare the oligomerization activity of the treated and untreated oxides under acid catalysis.

In one embodiment and in certain embodiments, the chemically-treated solid oxide is selected from oxygen and the 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, Consisting essentially of, or consist of a solid inorganic oxide comprising at least one element selected from oxygen and lanthanide or actinide elements; Alternatively, the chemically-treated solid oxide comprises at least one element selected from the group consisting of oxygen and at least one element selected from Group 4, 5, 6, 12, 13, or 14 of the Periodic Table, or at least one element selected from oxygen and lanthanide elements may comprise a solid inorganic oxide comprising (Hawley's Condensed Chemical Dictionary, 11 th Ed, John Wiley &Sons;.1995; Cotton, FA; Wilkinson, G .; Murillo; CA; and Bochmann; M. Advanced inorganic Chemistry, 6 ^th Ed., Wiley-Interscience, 1999). In some embodiments, the inorganic oxide is selected from the group consisting of oxygen and at least one of Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, , V, W, P, Y, Zn or Zr; Alternatively, the inorganic oxide comprises oxygen and at least one element selected from Al, B, Si, Ti, P, Zn or Zr.

In embodiments, the solid oxides used in the chemically-treated solid oxide include, but are not limited to, Al ₂ O ₃ , B ₂ O ₃ , BeO, Bi ₂ O ₃ , CdO, Co ₃ O ₄ , Cr ₂ O ₃ , CuO, Fe ₂ O ₃ , Ga ₂ O ₃ , La ₂ O ₃ , Mn ₂ O ₃ , MoO ₃ , NiO , P ₂ O ₅ , Sb ₂ O ₅ , SiO ₂ , SnO ₂ , SrO, ThO ₂ , TiO _{2 ,} V ₂ O ₅ , WO ₃ , Y ₂ O ₃ , ZnO, ZrO ₂ , Combinations thereof; Alternatively, Al ₂ O ₃ , B ₂ O ₃ , SiO ₂ , SnO ₂ , TiO _{2 ,} V ₂ O ₅ , WO ₃ , Y ₂ O ₃ , ZnO, ZrO ₂ , mixed oxides thereof, and combinations thereof; Alternatively, Al ₂ O ₃ , SiO _2, TiO _2, and ZrO _2, and others, including mixed oxides thereof, and combinations thereof. In some embodiments, the solid oxide used for the chemically-treated solid oxide is Al ₂ O ₃ ; Otherwise, B ₂ O ₃ ; Otherwise, BeO; Otherwise, Bi ₂ O ₃ ; Otherwise, CdO; Otherwise, Co ₃ O ₄ ; Otherwise, Cr ₂ O ₃ ; Otherwise, CuO; Otherwise, Fe ₂ O ₃ ; Otherwise, Ga ₂ O ₃ ; Otherwise, La ₂ O ₃ ; Otherwise, Mn ₂ O ₃ ; Otherwise, MoO ₃ ; Otherwise, NiO; Otherwise, P ₂ O ₅ ; Otherwise, Sb ₂ O ₅ ; Otherwise, SiO ₂ ; Otherwise, SnO _2; Otherwise, SrO; Otherwise, ThO _2; Alternatively, TiO ₂ ; Otherwise, V ₂ O ₅ ; Otherwise, WO ₃ ; Otherwise, Y ₂ O ₃ ; Otherwise, ZnO; Alternatively, Include or ZrO _2, or substantially consists of, it is made. In an embodiment, the mixed oxides used in the activator-support of the present invention include, but are not limited to, silica-alumina, silica-titania, silica-zirconia, zeolite, clay mineral, alumina-titania, alumina-zirconia, Aluminates; Alternatively, silica-alumina, silica-titania, silica-zirconia, alumina-titania, alumina-zirconia, and zinc-aluminate; Alternatively, silica-alumina, silica-titania, silica-zirconia, and alumina-titania are included. In some embodiments, the mixed oxide used in the activator-support of the present invention is silica-alumina; Otherwise, silica-titania; Alternatively, silica-zirconia; Otherwise, zeolite; Unlike clay minerals; Alternatively, alumina-titania; Alternatively, alumina-zirconia; Alternatively, and consist of, or consist of, a zinc-aluminate. In some embodiments, aluminosilicates, such as clay minerals, calcium aluminosilicates, or sodium aluminosilicates, are useful oxides that can be used in the activator-supports of the present invention.

In one aspect and in some embodiments of the present invention, the solid oxide material is chemically-treated in contact with at least one electron-attracting component (e.g., an electron-attracting anion source). Also, if necessary, the solid oxide material is chemically-treated with metal ions and then calcined to form a metal-containing or metal-impregnated chemically-treated solid oxide. Alternatively, the solid oxide material and the electron-attracting anion source may be contacted and fired at the same time. Methods in which an oxide is contacted with an electron-attracting component (e.g., an electron-attracting anion salt or an acid) include, but are not limited to, gelling, co-gelling, impregnating one compound into another compound, and the like. Typically, after the optional contact method, the contact mixture of oxide compound, electron-attracting anion, and, if present, metal ions is calcined.

 The electron-attracting component used in the oxide treatment may be any component which, upon treatment, increases the Lewis or Bronsted acidity of the solid oxide. In one embodiment, the electron-attracting component is an electron-attracting anion derived from a salt, acid, or other compound (e.g., a volatile organic compound) that serves as a source or precursor for an anion. In an embodiment, the electron-attracting anion is selected from the group consisting of, but not limited to, sulfates, bisulfates, fluorides, chlorides, bromides, iodides, fluoridesulfates, fluoroborates, phosphates, fluorophosphates, triflates, Acid salts, fluorotitanates, trifluoroacetates, triflates, and combinations thereof; Alternatively, it is possible to use a salt of a compound of the formula (I) in the form of a salt, such as a sulfate, a bisulfate, a fluoride, a chloride, a fluoride sulfate, a fluoride borate, a phosphate, a fluoride phosphate, a trifluctate, a triflate, a fluoride zirconate, Alternatively, fluorides, chlorides, bisulfates, sulfates, combinations thereof; Alternatively, sulfates, bisulfates, and combinations thereof; Alternatively, fluorides, chlorides, bromides, iodides, and combinations thereof; Alternatively, fluorosulfuric acid salts, fluoroboric acid salts, trifluoroacetic acid salts, triflates, fluorinated zirconates, fluorotitanic acid salts, trifluoroacetic acid salts, triflates, and combinations thereof; Unlike fluorides, chlorides, combinations thereof; Or alternatively, bisulfates, sulfates, combinations thereof. In some embodiments, the electron-attracting anion is selected from the group consisting of sulfate; Otherwise, bisulfate; Otherwise, fluoride; Otherwise, chloride; Otherwise, bromide; Otherwise, iodide; Otherwise, fluorosulfate; Otherwise, fluoroborate; Otherwise, phosphate; Otherwise, fluorophosphate; Alternatively, trifluoroacetate; Otherwise, a triplet; Otherwise, fluorinated zirconate; Otherwise, fluorotitanate; Alternatively, trifluoroacetate; Or alternatively, comprise, substantially consist of, or consist of a triplate. In addition, other ionic or non-ionic compounds that serve as sources of these electron-attracting anions may also be used in the present invention.

If the electron-withdrawing component comprises a salt of an electron-attracting anion, the counterion or cation of the salt may be any cation that allows the salt to return to the acid or decompose in the course of calcination. Factors that indicate the suitability of a particular salt provided as a source for the electron-attracting anion include the solubility of the salt in the desired solvent, the lack of reversibility of the cation, the ion-pair effect between the cation and the anion, the hygroscopicity imparted to the salt by the cation, But are not limited to, thermal stability of anions. In one aspect, the E-Examples of suitable cations in the salt of the draw anion include ammonium, trialkylammonium, tetraalkylammonium, ^{tetraalkylphosphonium, H +, [H (OEt} 2) 2] + , but not limited to, .

In addition, combinations of one or more different electron attracting anions can be used to tailor the specific acidity of the activator-support to a desired level, while changing the ratio. The combination of electron-attracting components may be contacted in any order, simultaneously or separately with the oxide material, and to provide the desired activator-support acidity. For example, one embodiment of the present invention uses two or more electron-attracting anion source compounds in two or more separate contacting steps. In this non-limiting embodiment where a chemically-treated solid oxide is produced, one example of such a process is prepared as follows. The selected solid oxide compound, or combination of oxide compounds, is contacted with a first electron-attracting anion source compound to form a first mixture, which is then calcined, and the calcined first mixture is then contacted with a second electron- A drag anion source compound to form a second mixture, and calcining the second mixture to form a treated solid oxide compound. In such a process, the first and second electron-attracting anion source compounds are typically different compounds although they may be the same compound.

In one aspect of the present invention, the solid oxide activator-support (chemically-treated solid oxide) can be prepared by the following process:

1) contacting a solid oxide compound and at least one electron-attracting anion source compound to form a first mixture; And

2) a first mixture calcining step to form a solid oxide activator-support.

In another embodiment of the present invention, the solid oxide activator-support (chemically-treated solid oxide) can be prepared by the following process:

1) contacting at least one solid oxide compound and a first electron-attracting anion source compound to form a first mixture;

2) firing a first mixture to produce a fired first mixture;

3) contacting the fired first mixture and the second electron-attracting anion source compound to form a second mixture; And

4) a second mixture calcining step to form a solid oxide activator-support.

The solid oxide activator-support is sometimes referred to simply as the treated solid oxide compound.

In another aspect of the invention, the chemically-treated solid oxide is formed or formed by contacting at least one solid oxide and at least one electron-attracting anion source compound compound, wherein at least one solid oxide compound is an electron- Before, during, or after the source contact, and substantially no aluminoxane and organoborate exist. In an embodiment, the chemically-treated solid oxide is formed or formed by contacting at least one solid oxide and at least one electron-attracting anion source compound compound, wherein at least one solid oxide compound is calcined prior to contact with the electron- And wherein substantially no aluminoxane and no organic borate are present; Alternatively, at least one solid oxide and at least one electron-attracting anion source compound compound are formed or formed by contact with at least one solid oxide and wherein at least one solid oxide compound can be calcined during the electron-attracting anion source contact, And no organic borate is present; Alternatively, at least one solid oxide compound may be produced or formed by contact of at least one solid oxide and at least one electron-attracting anion source compound, wherein at least one solid oxide compound may be calcined after contact with an electron-attracting anion source, There is no organic borate.

In one embodiment of the present invention, the solid oxide may be treated and dried and then fired continuously. The treated solid oxide firing is generally carried out in an ambient atmosphere; Otherwise, it is carried out in a dry ambient atmosphere. The solid oxide has a temperature of 200 to 900 占 폚; Alternatively 300 ° C to 800 ° C; Alternatively 400 [deg.] C to 700 [deg.] C; Alternatively, it may be calcined at 350 ° C to 550 ° C. The time for which the solid oxide is maintained at the firing temperature is from 1 minute to 100 hours; Alternatively from 1 hour to 50 hours; Alternatively 3 hours to 20 hours; Or alternatively, from 1 to 10 hours.

In addition, any type of suitable atmosphere may be applied during firing. Generally, firing is performed in an oxidizing atmosphere such as air. Alternatively, an inert atmosphere such as nitrogen or argon, or a reducing atmosphere such as hydrogen or carbon monoxide may be applied. In an embodiment, the firing atmosphere is air, nitrogen, argon, hydrogen, or carbon monoxide, or any combination thereof; Alternatively, nitrogen, argon, hydrogen, carbon monoxide, or any combination thereof; Otherwise, air; Otherwise, nitrogen; Otherwise, argon; Otherwise, hydrogen; Or alternatively, comprises, or substantially consists of, carbon monoxide.

In other and optional embodiments of the present invention, the solid oxide component used in the preparation of the chemically-treated solid oxide may have a pore volume greater than 0.1 cc / g. In another embodiment, the solid oxide component is greater than 0.5 cc / g; Alternatively, it may have a pore volume in excess of 1.0 cc / g. In another embodiment, the solid oxide component may have a surface area of 100 to 1000 m ² / g. In another embodiment, the solid oxide component comprises 200 to 800 m ² / g; Alternatively, it may have a surface area of 250 to 600 m ² / g.

The solid oxide material is treated with a halogen ion, a sulfate ion, or a combination thereof, and optionally a metal ion, and then calcined to provide a chemically-treated solid oxide in the form of a particulate solid. In one embodiment, the solid oxide material may be selected from the group consisting of a sulfate source (referred to as a sulfating agent), a phosphate source (referred to as a phosphorylating agent), an iodide ion source (referred to as an iodide), a bromine ion source (referred to as a brominating agent) , A fluorine ion source (referred to as a fluorinating agent), or any combination thereof, and is calcined and provided as a solid oxide activator. In another embodiment, useful acid activator-supports are selected from the group consisting of iodinated alumina, brominated alumina, chlorinated alumina, fluorinated alumina, sulfated alumina, phosphorylated alumina, iodized silica-alumina, brominated silica- alumina, chlorinated silica- Zirconia, chlorinated silica-zirconia, fluorinated silica-zirconia, sulfurized silica-zirconia, phosphorylated silica-zirconia, iodide, bromide, chloride, (For example, molecular sieves) treated with crosslinked clay (e.g., crosslinked montmorillonite), iodide, bromide, chloride, fluoride, sulfate, or phosphate treated with a fluoride, sulfate, or phosphate; or These acid activator-support Comprises a compound, or or substantially consists of, is made. In addition, any activator-support, as provided herein, can optionally be treated with metal ions.

Alternatively, useful acid activator-supports can be selected from the group consisting of chlorinated alumina, fluorinated alumina, sulfated alumina, phosphorylated alumina, chlorinated silica-alumina, fluorinated silica-alumina, sulfated silica-zeolite, fluorinated silica- Silica-zirconia, sulfate, fluoride, or chloride treated aluminophosphate, or any combination of these acidic activator-supports. In addition, the solid oxide may be treated with more than one electron-attracting anion, for example, the acidic activator-support may be an aluminophosphate treated with sulfates and fluorides or a silica treated with aluminosilicates, fluorides and chlorides Alumina; Or alumina treated with phosphates and fluorides.

In other and alternative embodiments, useful acid activator-supports are fluorinated alumina, sulfated alumina, fluorinated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, sulfated silica-zirconia, or phosphorus alumina, Or comprises, consists essentially of, or consists of any combination of two or more of the first, second, and third support. In another embodiment, useful acid activator-supports are iodinated alumina; Alternatively, alumina bromide; Otherwise, chlorinated alumina; Otherwise, fluorinated alumina; Otherwise, sulfated alumina; Otherwise, phosphorylated alumina; Alternatively, iodized silica-alumina; Alternatively, brominated silica-alumina; Alternatively, chlorinated silica-alumina; Alternatively, fluorinated silica-alumina; Alternatively, sulfated silica-alumina; Alternatively, phosphorylated silica-alumina; Alternatively, iodized silica-zirconia; Alternatively, brominated silica-zirconia; Alternatively, chlorinated silica-zirconia; Alternatively, fluorinated silica-zirconia; Otherwise, sulfurized silica-zirconia; Alternatively, phosphorylated silica-zirconia; Alternatively, crosslinked clays (e.g., crosslinked montmorillonite); Alternatively, iodinated cross-linked clay; Alternatively, brominated crosslinked clay; Otherwise, chlorinated crosslinked clay; Otherwise, fluorinated crosslinked clay; Otherwise, sulfated crosslinked clay; Alternatively, phosphorylated crosslinked clays; Alternatively, iodinated aluminophosphate; Alternatively, brominated aluminophosphate; Alternatively, chlorinated aluminophosphates; Alternatively, fluorinated aluminophosphates; Alternatively, sulfated aluminophosphates; Alternatively, phosphorylated aluminophosphates; Or any combination of these acidic activator-supports. Again, optional activator-supports described herein can optionally be treated with metal ions.

In one aspect of the invention, the chemically-treated solid oxide comprises, consists essentially of, or consists of a fluorinated solid oxide in the form of a particulate solid wherein the fluorine ion source is added to the solid oxide by treatment with the fluorinating agent. In another embodiment, fluorine ions are added to the solid oxide by forming a solid oxide slurry in a suitable solvent. In an embodiment, the solvent is an alcohol, water, or a combination thereof; Otherwise, alcohol; Alternatively, it can be water. Suitable alcohols in embodiments can have from 1 to 3 carbon alcohols with volatile and low surface tension. In another embodiment of the present invention, the solid oxide in the calcination step can be treated with a fluorinating agent. Any fluorinating agent that is provided as a fluoride source and can sufficiently contact the solid oxide during the firing step can be used. In a non-limiting embodiment, fluorinating agents that may be applied in the present invention include, but are not limited to, hydrofluoric acid (HF), ammonium fluoride (NH ₄ F), ammonium fluoride (NH ₄ HF ₂ ), ammonium tetrafluoroborate ₄ BF _4), ammonium silicon fluoride (6 silicate _{fluoride) ((NH 4) 2 SiF} 6), 6 of ammonium hexafluorophosphate (NH ₄ PF _6), and combinations thereof; Alternatively, it includes hydrofluoric acid (HF), ammonium fluoride (NH ₄ F), ammonium fluoride (NH ₄ HF ₂ ), ammonium tetrafluoroborate (NH ₄ BF ₄ ), and combinations thereof. In other non-limiting embodiments, the fluorinating agent is selected from the group consisting of hydrofluoric acid (HF); Alternatively, ammonium fluoride (NH ₄ F); Alternatively, ammonium fluoride (NH ₄ HF ₂ ); Alternatively, ammonium tetrafluoroborate (NH ₄ BF ₄ ); Alternatively, the rules ammonium fluoride (6 Silicate _{fluoride) ((NH 4) 2 SiF} 6); Or otherwise, ammonium hexafluorophosphate (NH ₄ PF _6), or the inclusion, or substantially it consists of, is made. For example, because of ease of use and availability, the neutralized ammonium NH ₄ HF ₂ can be used as a fluorinating agent.

In another embodiment of the present invention, the solid oxide may be treated with a fluorinating agent during the calcination step. Any fluorinating agent that can sufficiently contact the solid oxide during the firing step can be used. For example, in addition to the above-mentioned fluorinating agents, volatile organic fluorinating agents may be applied. Volatile organic fluorinating agents useful in this embodiment include, but are not limited to, freon, perfluorohexane, perfluorobenzene, perfluoromethane, trifluoroethanol, and combinations thereof. In some embodiments, the volatile fluorinating agent is selected from the group consisting of Freon; Otherwise, perfluorohexane; Otherwise, perfluorobenzene; Otherwise, perfluoromethane; Or alternatively, comprises, substantially consist of, or consist of trifluoroethanol. Gaseous hydrogen fluoride or fluorine itself can also be used for solid oxide fluorination in a given process. A common method of contacting solid oxides and fluorinating agents is to vaporize the fluorinating agent into a gas stream that flows the solid oxide during the firing process.

Similarly, in another aspect of the present invention, the chemically-treated solid oxide comprises, consists essentially of, or consists of a chlorinated solid oxide in the form of a particulate solid wherein the chlorine ion source supplies a solid oxide . Chloride ions are added to the solid oxide by forming a solid oxide slurry in a suitable solvent. In an embodiment, the solvent is an alcohol, water, or a combination thereof; Otherwise, alcohol; Alternatively, it can be water. Suitable alcohols in embodiments can have from 1 to 3 carbon alcohols with volatile and low surface tension. In another embodiment of the present invention, the solid oxide in the calcination step can be treated with a chlorinating agent. Any chlorinating agent which is provided as a chlorine source and which can sufficiently contact the solid oxide during the firing step can be used. In a non-limiting embodiment, volatile organic chlorinating agents may be used. In some embodiments, the volatile organic chlorinating agent is selected from the group consisting of, but not limited to, chlorine-containing chlorine, fluorine, chlorine, chlorine, Combinations. In some embodiments, the volatile organic chlorinating agent is a chlorine-containing freon; Alternatively, perchlorobenzene; Otherwise, chloromethane; Alternatively, dichloromethane; Otherwise, chloroform; Otherwise, carbon tetrachloride; Or alternatively, comprises, substantially consist of, or consist of trichloroethanol. Gaseous hydrogen chloride or chlorine itself can also be used in solid oxides in certain processes. A common method of contacting solid oxides and chlorinating agents is to vaporize the chlorinating agent into a gas stream that flows the solid oxide during the firing process.

In another embodiment, the chemically-treated solid oxide comprises, consists essentially of, or consists of a brominated solid oxide in the form of a particulate solid, wherein a source of bromine ion is added to the solid oxide by treatment with a brominating agent. Bromine ions are added to the solid oxide by forming a solid oxide slurry in a suitable solvent. In an embodiment, the brominating solvent may be an alcohol, water, or a combination thereof; Otherwise, alcohol; Alternatively, it can be water. Suitable alcohols in embodiments can have from 1 to 3 carbon alcohols with volatile and low surface tension. In another embodiment of the present invention, the solid oxide in the calcination step can be treated with a brominating agent. Any brominating agent which is provided as a source of bromide and which can sufficiently contact solid oxides during the firing step can be used. In a non-limiting embodiment, a volatile organic brominating agent may be used. In some embodiments, the volatile organic chlorinating agent is selected from the group consisting of but not limited to bromine containing freon, bromomethane, dibromomethane, tribromoethane, tetrabromoethylene, bromoform, carbon tetrabromide, tribromo Ethanol, or any combination thereof. In some embodiments, the volatile organic chlorinating agent is a bromine containing freon; Otherwise, bromomethane; Otherwise, dibromomethane; Otherwise, bromoform; Otherwise, carbon tetrabromide; Or alternatively, comprises, substantially consist of, or consist of tribromoethanol. Gaseous bromine hydrogen or bromine itself may also be used in solid oxides in certain processes. A common method of contacting solid oxides and brominating agents is to vaporize the brominating agent into a gas stream that flows the solid oxide during the firing process.

In one embodiment, the fluoride ion, chlorine ion, or bromine ion content present before solid oxide firing is generally from 2 to 50 wt%, wherein the wt% is based on the pre-firing solid oxide weight. In another embodiment, the fluoride or chloride ion content present before solid oxide calcination is 3 to 25 wt%; Otherwise, it is 4 to 20% by weight. After impregnation with the halide, the halogenated solid oxide can be dried by any method known in the art including, but not limited to, evaporation after suction filtration, drying under vacuum, spray drying and the like. In an embodiment, the calcining step can be initiated without drying the impregnated solid oxide.

In one aspect, silica-alumina, or a combination thereof, can be applied as a solid oxide material. The silica-alumina used in the preparation of the treated silica-alumina may have a pore volume exceeding 0.5 cc / g. In one embodiment, the pore volume is greater than 0.8 cc / g; Otherwise, it may exceed 1 cc / g. In addition, silica-alumina can have a surface area of greater than 100 m ² / g. In one embodiment, the surface area is greater than 250 m ² / g; Otherwise, it may exceed 350 m ² / g. Generally, the silica-alumina has an alumina content of 5 to 95%. In one embodiment, the alumina content of the silica-alumina is 5 to 50%; Alternatively, it may be from 8% to 30% by weight. In still other embodiments, the solid oxide component may comprise silica-free alumina, or alumina-free silica.

In another embodiment, the chemically-treated solid oxide comprises, consists essentially of, or consists of a sulfated solid oxide in the form of a particulate solid, wherein the sulfuric acid ion source is added as a solid oxide by treatment with the sulfurizing agent. Sulfated solid oxides include sulphates in the form of particulate solids and solid oxide components of any solid oxide component described (e.g., alumina or silica-alumina). Sulfated solid oxides can be further treated with metal ions, if necessary, and the sintered solid oxides can comprise metals. In one embodiment, the sulfated solid oxide comprises a sulfate and alumina; Alternatively, the sulfated solid oxides include sulfate and silica-alumina. In one aspect of the invention, the sulfated alumina is formed by a process of treating alumina or silica alumina with a sulfate source. Any sulphate source that can be in sufficient contact with the solid oxide can be used. In embodiments, the sulfate source includes, but is not limited to, a sulfate or sulfate ion containing salt (e.g., ammonium sulfate). In one embodiment, the present process can be performed by forming a solid oxide slurry in a suitable solvent. In an embodiment, the solvent is an alcohol, water, or a combination thereof; Otherwise, alcohol; Alternatively, it can be water. Suitable alcohols in embodiments can have from 1 to 3 carbon alcohols with volatile and low surface tension.

In one embodiment of the present invention and in certain embodiments, the sulfate ion content present prior to calcination is generally 0.5 parts by weight to 100 parts by weight sulfate ion per 100 parts by weight of solid oxide. In another embodiment, the sulfate ion content present prior to calcination is from about 1 part by weight to about 50 parts by weight sulfate ion relative to 100 parts by weight of solid oxide; Alternatively 5 to 30 parts by weight of sulfuric acid ions. After impregnation with the sulfate, the sulfurated solid oxides can be dried by any method known in the art including, but not limited to, evaporation after inhalation filtration, drying under vacuum, spray drying and the like. In an embodiment, the calcining step can be initiated without drying the impregnated solid oxide.

In another embodiment, the chemical-treated solid oxide is comprised, or substantially consists of, or is made up, wherein the phosphoric acid ion source is added as a solid oxide by the treatment with the phosphoric acid agent. The phosphorylated solid oxide comprises a phosphorus sulfate in particulate solid form and a solid oxide component of any of the solid oxide components described (e.g., alumina or silica-alumina). The phosphorylated solid oxide may further comprise a metal if required, the phosphorylated solid oxide further calcined with metal ions. In one aspect, the phosphorylated solid oxide is formed by a process that treats alumina or silica alumina with a phosphate source. Any phosphate source that can be in sufficient contact with the solid oxide can be used. In an embodiment, the phosphate source includes, but is not limited to, phosphoric acid, phosphorous acid, or phosphate ion containing salts (e.g., ammonium phosphate). In one embodiment, the present process can be performed by forming a solid oxide slurry in a suitable solvent. In an embodiment, the solvent is an alcohol, water, or a combination thereof; Otherwise, alcohol; Alternatively, it can be water. Suitable alcohols in embodiments can have from 1 to 3 carbon alcohols with volatile and low surface tension.

In one embodiment and in some embodiments of the present invention, the phosphate ion content present prior to firing is generally 0.5 to 100 parts by weight phosphoric acid ion per 100 parts by weight of solid oxide. In another embodiment, the phosphate ion content present prior to calcination is from about 1 part by weight to about 50 parts by weight phosphoric acid ion per 100 parts by weight of solid oxide; Alternatively, it is 5 to 30 parts by weight phosphoric acid ion. After being impregnated with phosphate, the phosphorylated solid oxide can be dried by any method known in the art including, but not limited to, evaporation after inhalation filtration, drying under vacuum, spray drying and the like. In an embodiment, the calcining step can be initiated without drying the impregnated solid oxide.

In addition to being treated with an electron-attracting component (e.g., a halide or sulfate ion), the solid inorganic oxide of the present invention may optionally be treated with a metal source. In an embodiment, the metal source may be a metal salt or a metal-containing compound. In one aspect of the invention, the metal salt or metal containing compound is added to the solid oxide in solution form or impregnated and fired to convert to a supported metal. Thus, the metal impregnated in the solid inorganic oxide is selected from the group consisting of zinc, titanium, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum, or combinations thereof; Alternatively, zinc, titanium, nickel, vanadium, silver, copper, tin, or any combination thereof; Alternatively, it comprises, consists essentially of, or consists of zinc, nickel, vanadium, tin, or any combination thereof. In an embodiment, the metal impregnated in the solid inorganic oxide is zinc; Otherwise, titanium; Otherwise, nickel; Otherwise, vanadium; Otherwise, silver; Otherwise, copper; Otherwise, gallium; Otherwise, annotation; Otherwise, tungsten; Or alternatively, comprise, consist essentially of, or consist of molybdenum. In some embodiments, zinc can be used to impregnate the solid oxide with good catalytic activity and low cost. Before, after, or simultaneously with the solid oxide being treated with an electron-attracting anion; Otherwise, before the solid oxide is treated with an electron-attracting anion; Alternatively, after the solid oxide is treated with an electron-attracting anion; Alternatively, the solid oxide can be treated with a metal salt or a metal-containing compound while the solid oxide is treated with an electron-attracting anion.

Any method of impregnating the solid oxide material with the metal may also be applied. Methods of contacting the solid oxide with a metal source (e.g., a metal salt or a metal-containing compound) include, but are not limited to, gelling, co-gelling, and impregnation of one compound with another. After an optional contact method, the contact mixture of solid oxide, electron-attracting anion, and metal ions is typically calcined. Alternatively, the solid oxide, electron-attracting anion source, and metal salt or metal-containing compound are contacted and fired at the same time.

In one embodiment, the metallocene or metallocene combination can be pre-contacted with the alpha olefin monomer and / or organoaluminum compound during the first period, before the mixture is contacted with the chemically-treated solid oxide. The present composition further comprising a chemically-treated solid oxide after the pre-contact mixture of the metallocene, alpha olefin monomer, and / or organoaluminum compound is contacted with the chemically-treated solid oxide is referred to as the & . The post-contact mixture may be placed during another second contact during the second period before being charged to the reactor in which the oligomerization process is performed.

Various chemical-treated solid oxides and chemically-treated solid oxide production methods that can be applied to the present invention have been reported. The following United States patents and published United States patent applications provide such disclosures, each of which is incorporated herein by reference in its entirety: 6,107,230, 6,165,929, 6,294,494, 6,300,271, 6,316,553, 6,355,594, 6,376,415, 6,391,816, 6,395,666 , 6,524,987, 6,548,441, 6,750,302, 6,831,141, 6,936,667, 6,992,032, 7,601,665, 7,026,494, 7,148,298, 7,470,758, 7,517,939, 7,576,163, 7,294,599, 7,629,284, 7,501,372, 7,041,617, 7,226,886, 7,199,073, 7,312,283, 7,619,047, and 2010/0076167.

Organoaluminum compound

One aspect of the present invention provides an oligomerization process (or PAO process) comprising contacting a catalyst system comprising an alpha olefin monomer and a metallocene. In an embodiment, the catalyst system may further comprise an activator. In certain embodiments provided herein, the activator may comprise a solid oxide chemically treated with an electron attracting anion. In another aspect of certain embodiments provided herein, the catalyst system may comprise at least one organoaluminum compound, either alone or in combination with a chemically-treated solid oxide and / or any other activator (s) have. In some embodiments, the catalyst system comprises, consists essentially of, or consists of a metallocene, a first activator comprising a chemically-treated solid oxide, and a second activator comprising an organoaluminum compound. In one aspect, organoaluminum compounds that can be used in the catalyst system of the present invention include, but are not limited to, compounds having the formula:

_{^{Al (X 10) n (X}} 11) 3 -n.

In an embodiment, each X ¹⁰ is independently a C ₁ to C ₂₀ hydrocarbyl group; Alternatively, a C ₁ to C ₁₀ hydrocarbyl group; Alternatively, a C ₆ to C ₂₀ aryl group; Alternatively, a C ₆ to C ₁₀ aryl group; Otherwise, a C ₁ to C ₂₀ alkyl group; Alternatively, a C ₁ to C ₁₀ alkyl group; Or alternatively may be a C ₁ to C ₅ alkyl group. In an embodiment, each X ¹¹ is independently a halide, a hydride, or a C ₁ to C ₂₀ hydrocarboxy group (also referred to as a hydrocarboxy group); Alternatively, a halide, a hydride, or a C ₁ to C ₁₀ hydrocarboxy group; Alternatively, a halide, a hydride, or a C ₆ to C ₂₀ aryloxyd group (also referred to as an aroxide or an aroxy group); Alternatively, a halide, a hydride, or a C ₆ to C ₁₀ aryloxyd group; Alternatively, a halide, a hydride, or a C ₁ to C ₂₀ alkoxy group (also referred to as an alkoxy group); Alternatively, a halide, a hydride, or a C ₁ to C ₁₀ alkoxy group; Alternatively, a halide, a hydride, or a C ₁ to C ₅ alkoxy group; Otherwise, halide; Unlike hydrides; Alternatively, a C ₁ to C ₂₀ hydrocarboxy group; Alternatively, a C ₁ to C ₁₀ hydrocarboxy group; Alternatively, a C ₆ to C ₂₀ aryloxyd group; Alternatively, a C ₆ to C ₁₀ aryloxyd group; A C ₁ to C ₂₀ alkoxy group; Otherwise, a C ₁ to C ₁₀ alkoxy group; Alternatively, it may be a C ₁ to C ₅ alkoxy group. In an embodiment, n is a number from 1 to 3 (integer or non-integer); Alternatively, about 1.5, otherwise, or otherwise, can be 3.

In an embodiment, the formula _{^{Al (X 10) n (X}} 11) 3 - each of the alkyl groups of the organoaluminum compound having _n (s) is independently a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl A t-butyl group, or an octyl group; Alternatively, it may be a methyl group, an ethyl group, a butyl group, a hexyl group, or an octyl group. In some embodiments, each alkyl group (s) of the organoaluminum compound having the formula Al (X ¹⁰ ) _n (X ¹¹ ) _{3 - n} is independently selected from the group consisting of methyl, ethyl, n-propyl, A butyl group, an n-hexyl group, or an n-octyl group; Alternatively, a methyl group, an ethyl group, an n-butyl group, or an iso-butyl group; Otherwise, a methyl group; Otherwise, ethyl; An n-propyl group; An n-butyl group; An iso-butyl group; Otherwise, n-hexyl; Or alternatively an n-octyl group. In an embodiment, the formula _{^{Al (X 10) n (X}} 11) 3 - each aryl of the organoaluminum compounds having the _n groups to the phenyl group or substituted phenyl group independently; Otherwise, phenyl group; Or alternatively, a substituted phenyl group.

In an embodiment, the formula _{^{Al (X 10) n (X}} 11) 3 - each of the organoaluminum halide compound having _n may be independently fluoride, chloride, bromide, iodide. In some embodiments, the formula _{^{Al (X 10) n (X}} 11) 3 - each of the organoaluminum halide compound having _n are independently fluoride; Otherwise, chloride; Otherwise, bromide; Or alternatively it may be iodide.

In an embodiment, the formula _{^{Al (X 10) n (X}} 11) 3 - n each alkoxide independently methoxy group of organoaluminum compounds with, an ethoxy group, a propoxy group, a butoxy group, pentoxy group, heksok time, heptok A period, or an octoxy group; Alternatively, it may be a methoxy group, an ethoxy group, a butoxy group, a hexoxy group, or an octoxy group. In some embodiments, the alkoxy group is independently selected from the group consisting of methoxy, ethoxy, n-propoxy, n-butoxy, iso-butoxy, n- Alternatively, a methoxy group, an ethoxy group, an n-butoxy group, or an iso-butoxy group; Otherwise, a methoxy group; Otherwise, the ethoxy group; Otherwise, the n-propoxy group; An n-butoxy group; Otherwise, the iso-butoxy group; Otherwise, the n-hexyl period; Or alternatively an n-octoxy group. Example In the formula _{^{Al (X 10) n (X}} 11) 3-n , each of the aryl allyl hydroxy lifting independently of an organoaluminum compound with a seed or a substituted phenoxide; Otherwise, phenoxide; Or alternatively, a substituted phenoxide.

In embodiments, the organoaluminum compounds applicable in any embodiment or embodiment of the present invention include trialkylaluminum, dialkylaluminum halides, alkylaluminum dihalides, dialkylaluminum alkoxides, alkylaluminum dialkoxides, dialkylaluminum hydrides , Alkyl aluminum dihydrate, and combinations thereof. In another embodiment, the organoaluminum compounds applicable in any embodiment or embodiment of the present invention include trialkylaluminum, dialkylaluminum halide, alkylaluminum dihalide, and combinations thereof; Alternatively, trialkylaluminum; Alternatively, dialkylaluminum halides; Alternatively, an alkyl aluminum dihalide; Alternatively, dialkyl aluminum alkoxide; Alternatively, alkyl aluminum dialkoxides; Alternatively, dialkyl aluminum hydride; Or alternatively, comprise, consist essentially of, or consist of an alkyl aluminum dihydrate. In still other embodiments, the organoaluminum compounds applicable in any embodiment or embodiment of the present invention include trialkylaluminum, alkylaluminum halide, or combinations thereof; Alternatively, trialkylaluminum; Or alternatively, comprise, consist essentially of, or consist of an alkyl aluminum halide.

In a non-limiting example, useful trialkylaluminum compounds include trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, or mixtures thereof. In some non-limiting embodiments, useful trialkyl aluminum compounds include trimethylaluminum, triethylaluminum, tripropylaluminum, tri-n-butylaluminum, tri-isobutylaluminum, trihexylaluminum, tri- These mixtures; Alternatively, triethyl aluminum, tri-n-butyl aluminum, tri-isobutyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, or mixtures thereof; Alternatively, triethyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, or mixtures thereof. In other non-limiting embodiments, useful trialkylaluminum compounds include trimethylaluminum; Alternatively, triethylaluminum; Alternatively, tripropylaluminum; Alternatively, tri-n-butyl aluminum; Alternatively, tri-isobutylaluminum; Alternatively, tri-n-hexyl aluminum; Or alternatively, tri-n-octylaluminum.

In a non-limiting example, useful alkyl aluminum halides may include diethyl aluminum chloride, diethyl aluminum bromide, ethyl aluminum dichloride, ethyl aluminum sesquichloride, and mixtures thereof. In some non-limiting embodiments, useful alkyl aluminum halides may include diethyl aluminum chloride, ethyl aluminum dichloride, ethyl aluminum sesquichloride, and mixtures thereof. In other non-limiting embodiments, useful alkyl aluminum halides include diethyl aluminum chloride; Alternatively, diethylaluminum bromide; Alternatively, ethyl aluminum dichloride; Alternatively, it may be ethyl aluminum sesquichloride.

In one aspect, the present invention provides pre-contact metallocene and at least one organoaluminum compound and olefin monomer to form a pre-contact mixture prior to formation of an active catalyst by pre-contacting mixture and solid oxide activator-support contact . When a catalyst system is prepared in this manner, typically some, but not necessarily, some organoaluminum compounds are added to the pre-contact mixture and some of the other organoaluminum compounds are removed after contact with the solid oxide activator, Is added to the contact mixture. However, all organoaluminum compounds can be used in the pre-contact or post-contact stages to produce catalyst systems. Alternatively, all catalyst system components may be contacted in a single step.

In addition, more than one organoaluminum compound may be used in the pre-contact or post-contact stages. When the organoaluminum compound is added in multiple stages, the content of organoaluminum compounds described herein is dependent on the organoaluminum compound content used in both the pre- and post-contact mixture, and the total amount of any additional organoaluminum compound added to the oligomerization reactor It is the content. Thus, the total content of organoaluminum compounds is disclosed regardless of whether a single or more than one organoaluminum compound is used. In another embodiment, triethyl aluminum (TEA) or triisobutyl aluminum is a typical organoaluminum compound used in the present invention. In some embodiments, the organoaluminum compound is triethylaluminum; Or alternatively it may be triisobutylaluminum.

In one embodiment and in certain embodiments described herein wherein the catalyst system employs an organoaluminum compound, the metal mole ratio of aluminum to metallocene of the organoaluminum compound is greater than 0.1: 1 (Al: metal of metallocene); Otherwise, greater than 1: 1; Alternatively, greater than 10: 1; Alternatively, may exceed 50: 1. In some embodiments where the catalyst system employs an organoaluminum compound, the metal mole ratio of aluminum to metallocene of the organoaluminum compound is from 0.1: 1 to 100,000: 1 (Al: metal of metallocene); Alternatively from 1: 1 to 10,000: 1; Alternatively from 10: 1 to 1,000: 1; Alternatively from 50: 1 to 500: 1. When the metallocene includes a specific metal (for example, Zr), the molar ratio is Al: a specific metal molar ratio (for example, Al: Zr molar ratio).

In other embodiments and in certain embodiments described herein wherein the catalyst system employs an organoaluminum compound, the metal mole ratio of the aluminum-carbon bonds to the metallocene of the organoaluminum compound is selected from the group consisting of Al-C bonds: ) Greater than 0.1: 1; Otherwise, greater than 1: 1; Alternatively, greater than 10: 1; Alternatively, may exceed 50: 1. Catalyst System Utilizing Organoaluminum Compounds In some embodiments, the metal molar ratio of aluminum-carbon bonds to metallocenes of the organoaluminum compound is from 0.1: 1 to 100,000: 1 (Al-C bonds: metal of metallocene) ; Alternatively from 1: 1 to 10,000: 1; Alternatively from 10: 1 to 1,000: 1; Alternatively from 50: 1 to 500: 1. When the metallocene comprises a specific metal (for example Zr), the ratio is Al-C bond: specific metal ratio (for example Al-C bond: Zr mole ratio).

Aluminoxane

In one aspect, the present invention encompasses a catalyst system comprising at least one metallocene and at least one activator. The invention also encompasses an oligomerization process, which comprises contacting the catalyst system (or PAO production process, which comprises alpha olefin monomers and metallocenes). In an embodiment, the catalyst system may further comprise an activator. Aluminoxanes are otherwise referred to as poly (hydrocarbyl aluminum oxide), organic aluminoxane, or alumoxane. In other and optional embodiments provided herein, the catalyst system may comprise at least one aluminoxane compound, either alone or in combination with a chemically-treated solid oxide and / or any other activator (s) have. A chemically-treated solid oxide, wherein aluminoxane is described and not limited herein; Or alternatively, in combination with chemically-treated solid oxides and other activators. In some embodiments, the catalyst system comprises, consists essentially of, or consists of a metallocene, a first activator comprising a chemically-treated solid oxide, and a second activator comprising alumoxane.

Alumoxane compounds that may be used in the catalyst systems of the present invention include, but are not limited to, oligomeric compounds. The oligomeric aluminoxane compounds include linear, cyclic, or cage structures, or mixtures of the three. The oligomeric aluminoxane, whether an oligomeric or polymeric compound, has the following repeating unit formula:

; 여기에서

; From here

R ¹² is a linear or branched alkyl group. The linear aluminoxane has the formula:

; 여기에서

; From here

R ¹² is a linear or branched alkyl group encompassed by the present invention. Alkyl groups for the organoaluminum compound formula Al (X ¹⁰ ) _n (X ¹¹ ) _{3 -n} are independently described herein and these alkyl groups are not limited, and are applied to further describe aluminoxane having formula I. Generally, in alumoxane, n is greater than 1 on average; Alternatively, it may exceed two. In an embodiment, n is 2 to 15; Alternatively, from 3 to 10 ranges or ranges.

Also, the aluminoxane may have a cage structure of the formula R ^t _{5 m + α} R ^b _{m - α} A l _{4 m} O _{3 m} , Where m is 3 or 4 and _{α = n Al (3) -} n O (2) + n O (4); n _{Al (3)} is the three-coordinate aluminum atoms, n _{O (2)} will be the two coordinate oxygen atoms, n _{O (4)} is coordinated with four oxygen atoms, R ^t is a terminal alkyl group, and R ^b Is a bridged alkyl group; Wherein R is a linear or branched alkyl of 1 to 10 carbon atoms. Alkyl groups for the organoaluminum compound formula Al (X ¹⁰ ) _n (X ¹¹ ) _{3 -n} are independently described herein and these alkyl groups are not limited and include, but are not limited to, R ^t _{5 m + α} R ^b _{m - α} A l _{4 m} O Lt; _{RTI ID = 0.0 &gt} ; _{3 m &lt} ; / _{RTI &gt} ; cage structure

In a non-limiting example, useful aluminoxanes are selected from the group consisting of methyl aluminoxane (MAO), ethyl aluminoxane, reformed methyl aluminoxane (MMAO), n-propyl aluminoxane, iso- butylaluminoxane, isobutylaluminoxane, isobutylaluminoxane, isobutylaluminoxane, sec-butylaluminoxane, sec-butylaluminoxane, isobutylaluminoxane, Or mixtures thereof; In some non-limiting embodiments, useful aluminoxanes may include methyl aluminoxane (MAO), reformed methyl aluminoxane (MMAO), isobutyl aluminoxane, t-butyl aluminoxane, or mixtures thereof. In other non-limiting embodiments, useful aluminoxanes include methyl aluminoxane (MAO); Otherwise, ethylaluminoxane; Alternatively, reformed methyl aluminoxane (MMAO); Alternatively, n-propylaluminoxane; Alternatively, iso-propyl-aluminoxane; Alternatively, n-butylaluminoxane; Alternatively, sec-butylaluminoxane; Alternatively, iso-butylaluminoxane; Alternatively, t-butylaluminoxane; Alternatively, 1-pentyl-aluminoxane; Alternatively, 2-pentylaluminoxane; Alternatively, 3-pentyl-aluminoxane; Alternatively, iso-pentyl-aluminoxane; Or alternatively, neopentylaluminoxane.

Although organic aluminoxanes having different types of "R" groups such as R ¹² are encompassed by the present invention, methylaluminoxane (MAO), ethylaluminoxanic acid, or isobutylaluminoxane is also included in the catalyst system of the present invention, Can be used. These aluminoxanes are each produced from trimethylaluminum, triethylaluminum, or triisobutylaluminum, and are sometimes referred to as poly (methyl aluminum oxide), poly (ethyl aluminum oxide), and poly (isobutyl aluminum oxide), respectively. It is also within the scope of the present invention to use aluminoxanes in combination with trialkylaluminum as disclosed in U.S. Patent No. 4,794,096, which is incorporated herein by reference in its entirety.

The present invention aluminoxane formulas ^{(-Al (R 12) O-)} n and ^{R 12 (-Al (R 12)} O-) n Al (R 12) taking into account the various levels in the _2, preferably n is At least about three. However, depending on the method of preparing, storing and using the organic aluminoxane, the n value can be varied in a single sample of aluminoxane, and the combination of these organic aluminoxanes is included in the methods and compositions of the present invention.

In the production of a catalyst system comprising aluminoxane, the molar ratio of aluminum to metallocene of the aluminoxane in the catalyst system is greater than 0.1: 1 (Al: the metal of the metallocene); Otherwise, greater than 1: 1; Alternatively, greater than 10: 1; Alternatively, may exceed 50: 1. In an embodiment, the metal molar ratio of aluminum to metallocene of aluminoxane in the catalyst system is from 0.1: 1 to 100,000: 1 (Al: metal of metallocene); Alternatively from 1: 1 to 10,000: 1; Alternatively from 10: 1 to 1,000: 1; Alternatively from 50: 1 to 500: 1. When the metallocene contains a specific metal (e.g. Zr), the ratio is Al: specific metal ratio (e.g. Al: Zr molar ratio). In one embodiment, the aluminoxane content added to the oligomerization zone is from 0.01 mg / L to 1000 mg / L; Alternatively 0.1 mg / L to 100 mg / L; Alternatively, or in the range of 1 mg / L to 50 mg / L.

Organic aluminoxanes may be prepared by a variety of methods well known in the art of organoaluminoxane manufacture disclosed in U.S. Patent Nos. 3,242,099 and 4,808,561, which are incorporated herein by reference in their entirety. An example of a method for producing aluminoxane is as follows. The water dissolved in the inert organic solvent reacts with an aluminum alkyl compound such as AlR ₃ to form the desired organic aluminoxane compound. Without intending to be bound by this statement, it is believed that this synthesis method can provide a mixture of both linear and cyclic (R-Al-O) _n aluminoxane species, all of which are encompassed by the present invention. Alternatively, the organoaluminoxane can be prepared by reacting an aluminum alkyl compound such as AlR ₃ with a hydrate such as a hydrated copper sulphate in an inert organic solvent.

Other catalyst components may be contacted with the aluminoxane in a solvent that is substantially inert to the reactants, intermediates, and products of the active phase. The catalyst system formed in this manner can be recovered by methods known to those skilled in the art including, but not limited to, filtration, or the catalyst system can be introduced into the oligomerization reactor without separation.

Organic zinc  compound

As disclosed, one aspect of the present invention provides an oligomerization process (or PAO process) comprising contacting a catalyst system comprising an alpha olefin monomer and a metallocene. In an embodiment, the catalyst system may further comprise an activator. In certain embodiments provided herein, the activator may comprise a solid oxide chemically treated with an electron attracting anion. In another aspect of certain embodiments provided herein, the catalyst system may comprise at least one organozinc compound in combination with, or alone, a chemically-treated solid oxide and / or any other activator (s) have. In some embodiments, the catalyst system comprises, consists essentially of, or consists of a metallocene, a first activator comprising a chemically-treated solid oxide, and a second activator comprising an organozinc compound. In one embodiment, the organozinc compounds that may be used in the catalyst system of the present invention include, but are not limited to, compounds having the formula:

Zn (X ¹² ) _p (X ¹³ ) _{2 -p} .

In an embodiment, each X ¹² is independently a C ₁ to C ₂₀ hydrocarbyl group; Alternatively, a C ₁ to C ₁₀ hydrocarbyl group; Alternatively, a C ₆ to C ₂₀ aryl group; Alternatively, a C ₆ to C ₁₀ aryl group; Otherwise, a C ₁ to C ₂₀ alkyl group; Alternatively, a C ₁ to C ₁₀ alkyl group; Or alternatively may be a C ₁ to C ₅ alkyl group. In an embodiment, each X ¹³ is independently a halide, a hydride, or a C ₁ to C ₂₀ hydrocarboxy group; Alternatively, a halide, a hydride, or a C ₁ to C ₁₀ hydrocarboxy group; Alternatively, a halide, a hydride, or a C ₆ to C ₂₀ aryloxyd group; Alternatively, a halide, a hydride, or a C ₆ to C ₁₀ aryloxyd group; Alternatively, a halide, a hydride, or a C ₁ to C ₂₀ alkoxy group; Alternatively, a halide, a hydride, or a C ₁ to C ₁₀ alkoxy group; Alternatively, a halide, a hydride, or a C ₁ to C ₅ alkoxy group; Otherwise, halide; Unlike hydrides; Alternatively, a C ₁ to C ₂₀ hydrocarboxy group; Alternatively, a C ₁ to C ₁₀ hydrocarboxy group; Alternatively, a C ₆ to C ₂₀ aryloxyd group; Alternatively, a C ₆ to C ₁₀ aryloxyd group; A C ₁ to C ₂₀ alkoxy group; Otherwise, a C ₁ to C ₁₀ alkoxy group; Alternatively, it may be a C ₁ to C ₅ alkoxy group. In an embodiment, p is a number from 1 to 2 (integer or non-integer); Alternatively, 1, otherwise, or otherwise, may be 2. The alkyl group, aryl group, alkoxide group, aryloxid group and halide are independently represented by the potential groups for X ¹⁰ and X ¹¹ of the organoaluminum compound having the formula Al (X ¹⁰ ) _n (X ¹¹ ) _{3 - n} , (X ¹² ) _p (X ¹³ ) _{2 - p} , which is used in the aspects and embodiments described in the present invention, is not limited to these alkyl groups, aryl groups, alkoxy groups, aryloxid groups, Can be applied to describe organozinc compounds.

In other embodiments and in certain embodiments of the invention, useful organozinc compounds include dimethyl zinc, diethyl zinc, dipropyl zinc, dibutyl zinc, dineopentyl zinc, di (trimethylsilylmethyl) zinc, any combination thereof; Otherwise, dimethylzinc; Diethylzinc, in contrast; Otherwise, dipropyl zinc; Otherwise, dibutyl zinc; Diene pentyl zinc, alternatively; Or alternatively, comprises, consists essentially of, or consists of di (trimethylsilylmethyl) zinc.

In one embodiment and in any of the embodiments described herein wherein the catalyst system utilizes an organozinc compound, the metal mole ratio of the organozinc compound to the metallocene (Zn: the metal of the metallocene) is greater than 0.1: 1; Otherwise, greater than 1: 1; Alternatively, greater than 10: 1; Alternatively, may exceed 50: 1. In some embodiments where the catalyst system utilizes an organozinc compound, the metal mole ratio of the organozinc compound to the metallocene (Zn: the metal of the metallocene) is from 0.1: 1 to 100,000: 1; Alternatively from 1: 1 to 10,000: 1; Otherwise 10: 1 to 1,000: 1; Alternatively from 50: 1 to 500: 1. When the metallocene contains a specific metal (for example Zr), the ratio is Zn: specific metal ratio (for example Zn: Zr molar ratio).

Organomagnesium  compound

Another aspect of the present invention provides an oligomerization process (or PAO process) comprising contacting a catalytic system comprising an alpha olefin monomer and a metallocene. In an embodiment, the catalyst system may further comprise an activator. In certain embodiments provided herein, the activator may comprise a solid oxide chemically treated with an electron attracting anion. In another aspect of certain embodiments provided herein, the catalyst system may comprise at least one organomagnesium compound in combination with, or alone, a chemically-treated solid oxide and / or any other activator (s) have. In some embodiments, the catalyst system comprises, consists essentially of, or consists of a metallocene, a first activator comprising a chemically-treated solid oxide, and a second activator comprising an organomagnesium compound. In one embodiment, the organomagnesium compounds that can be used in the catalyst system of the present invention include, but are not limited to, compounds having the formula:

Mg (X ¹⁷ ) _q (X ¹⁸ ) _{2 -q} .

In an embodiment, each X ¹⁷ is independently a C ₁ to C ₂₀ hydrocarbyl group; Alternatively, a C ₁ to C ₁₀ hydrocarbyl group; Alternatively, a C ₆ to C ₂₀ aryl group; Alternatively, a C ₆ to C ₁₀ aryl group; Otherwise, a C ₁ to C ₂₀ alkyl group; Alternatively, a C ₁ to C ₁₀ alkyl group; Or alternatively may be a C ₁ to C ₅ alkyl group. In an embodiment, each X ¹⁸ is independently a halide, a hydride, or a C ₁ to C ₂₀ hydrocarboxy group; Alternatively, a halide, a hydride, or a C ₁ to C ₁₀ hydrocarboxy group; Alternatively, a halide, a hydride, or a C ₆ to C ₂₀ aryloxyd group; Alternatively, a halide, a hydride, or a C ₆ to C ₁₀ aryloxyd group; Alternatively, a halide, a hydride, or a C ₁ to C ₂₀ alkoxy group; Alternatively, a halide, a hydride, or a C ₁ to C ₁₀ alkoxy group; Alternatively, a halide, a hydride, or a C ₁ to C ₅ alkoxy group; Otherwise, halide; Unlike hydrides; Alternatively, a C ₁ to C ₂₀ hydrocarboxy group; Alternatively, a C ₁ to C ₁₀ hydrocarboxy group; Alternatively, a C ₆ to C ₂₀ aryloxyd group; Alternatively, a C ₆ to C ₁₀ aryloxyd group; A C ₁ to C ₂₀ alkoxy group; Otherwise, a C ₁ to C ₁₀ alkoxy group; Alternatively, it may be a C ₁ to C ₅ alkoxy group. In an embodiment, q is a number from 1 to 2 (integer or non-integer); Alternatively, 1, otherwise, or otherwise, may be 2. The alkyl group, aryl group, alkoxide group, aryloxid group and halide are independently represented by the potential groups for X ¹⁰ and X ¹¹ of the organoaluminum compound having the formula Al (X ¹⁰ ) _n (X ¹¹ ) _{3 - n} , with _{q -,} and these alkyl group, an aryl group, an alkoxy deugi, aryl, hydroxide group, and formula halide is used in the aspects and embodiments described in the present invention is not limited _{^{Mg (X 17) q (X}} 18) 2 Can be applied to describe organomagnesium compounds. By way of example, the organomagnesium compound may comprise or be selected from dihydrocarbylmagnesium compounds, Grignard reagents, and similar compounds such as alkoxy magnesium alkyl compounds.

In other embodiments and in certain embodiments of the present invention, useful organomagnesium compounds are selected from the group consisting of dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, dineopentylmagnesium, di (trimethylsilylmethyl) magnesium, methylmagnesium chloride, ethyl Magnesium bromide, magnesium bromide, propyl magnesium bromide, butyl magnesium bromide, neopentyl magnesium bromide, trimethylsilyl chloride, trimethylsilylmethyl chloride, methylmagnesium bromide, ethylmagnesium bromide, propylmagnesium chloride, butylmagnesium chloride, Methylmagnesium bromide, methylmagnesium iodide, ethylmagnesium iodide, propylmagnesium iodide, butylmagnesium iodide, neopentylmagnesium iodide, trimethylsilylmethylmagnesium iodide, methylmagnesium ethoxide, ethylmagnesium Butyl magnesium ethoxide, neopentyl magnesium ethoxide, trimethylsilylmethyl magnesium ethoxide, methyl magnesium propoxide, ethyl magnesium propoxide, propyl magnesium propoxide, butyl magnesium propoxide, propyl magnesium acetate, propyl magnesium acetate, Neopentyl magnesium phenoxide, neopentyl magnesium propoxide, trimethyl silyl methyl magnesium propoxide, methyl magnesium phenoxide, ethyl magnesium phenoxide, propyl magnesium phenoxide, butyl magnesium phenoxide, neopentyl magnesium phenoxide, trimethylsilylmethyl magnesium phenoxide, Any combination; Otherwise, dimethylmagnesium; Diethyl magnesium; Di- propylmagnesium; Otherwise, dibutylmagnesium; Otherwise, dinneopentylmagnesium; Di (trimethylsilylmethyl) magnesium; Otherwise, methylmagnesium chloride; Otherwise, ethylmagnesium chloride; Otherwise, propyl magnesium chloride; Otherwise, butylmagnesium chloride; Alternatively, neopentylmagnesium chloride; Alternatively, trimethylsilylmethylmagnesium chloride; Alternatively, methylmagnesium bromide; Alternatively, ethylmagnesium bromide; Alternatively, propylmagnesium bromide; Alternatively, butylmagnesium bromide; Alternatively, neopentylmagnesium bromide; Alternatively, trimethylsilylmethylmagnesium bromide; Otherwise, methylmagnesium iodide; Otherwise, ethylmagnesium iodide; Alternatively, propyl magnesium iodide; Otherwise, butylmagnesium iodide; Alternatively, neopentylmagnesium iodide; Alternatively, trimethylsilylmethylmagnesium iodide; Otherwise, methylmagnesium ethoxide; Alternatively, ethyl magnesium ethoxide; Alternatively, propylmagnesium ethoxide; Otherwise, butylmagnesium ethoxide; Alternatively, neopentyl magnesium ethoxide; Alternatively, trimethylsilylmethylmagnesium ethoxide; Alternatively, methyl magnesium propoxide; Alternatively, ethyl magnesium propoxide; Alternatively, propylmagnesium propoxide; Alternatively, butylmagnesium propoxide; Alternatively, neopentyl magnesium propoxide; Alternatively, trimethylsilylmethyl magnesium propoxide; Alternatively, methylmagnesium phenoxide; Alternatively, ethyl magnesium phenoxide; Alternatively, propylmagnesium phenoxide; Otherwise, butylmagnesium phenoxide; Alternatively, neopentylmagnesium phenoxide; Or alternatively, comprise, substantially consist of, or consist of trimethylsilylmethyl magnesium phenoxide.

In one embodiment and in any of the embodiments described herein wherein the catalyst system employs an organomagnesium compound, the metal mole ratio of the organomagnesium compound to the metallocene is greater than 0.1: 1 (Mg: the metal of the metallocene); Otherwise, greater than 1: 1; Alternatively, greater than 10: 1; Alternatively, may exceed 50: 1. In some embodiments where the catalyst system employs an organomagnesium compound, the metal mole ratio of the organomagnesium compound to the metallocene is from 0.1: 1 to 100,000: 1 (Mg: the metal of the metallocene); Alternatively from 10: 1 to 10,000: 1; Alternatively from 10: 1 to 1,000: 1; Alternatively from 50: 1 to 500: 1. When the metallocene contains a specific metal (such as Zr), the ratio is Mg: specific metal ratio (for example, Mg: Zr molar ratio).

Organolithium  compound

Another aspect of the present invention provides an oligomerization process (or PAO process) comprising contacting a catalytic system comprising an alpha olefin monomer and a metallocene. In an embodiment, the catalyst system may further comprise an activator. In certain embodiments provided herein, the activator may comprise a solid oxide chemically treated with an electron attracting anion. In another aspect of certain embodiments provided herein, the catalyst system may comprise at least one organolithium compound in combination with, or alone, a chemically-treated solid oxide and / or any other activator (s) have. In some embodiments, the catalyst system comprises, consists essentially of, or consists of a metallocene, a first activator comprising a chemically-treated solid oxide, and a second activator comprising an organolithium compound. In one embodiment, the organolithium compounds that may be used in the catalyst system of the present invention include, but are not limited to, compounds having the formula:

Li (X ¹⁹ ).

In an embodiment, X ¹⁹ is a C ₁ to C ₂₀ hydrocarbyl group or a hydride thereof; Alternatively, a C ₁ to C ₁₀ hydrocarbyl group; Alternatively, a C ₆ to C ₂₀ aryl group; Alternatively, a C ₆ to C ₁₀ aryl group; Otherwise, a C ₁ to C ₂₀ alkyl group; Alternatively, a C ₁ to C ₁₀ alkyl group; Otherwise, a C ₁ to C ₅ alkyl group; Alternatively, it can be a hydride. Alkyl groups and aryl groups are independently described herein as potential groups for X ¹⁰ and X ¹¹ of an organoaluminum compound having the formula Al (X ¹⁰ ) _n (X ¹¹ ) _{3 - n} , wherein these alkyl groups and aryl groups are not limited, Can be applied to describe organolithium compounds having the formula Li (X ¹⁹ ) used in the described embodiments and embodiments.

In other embodiments and in certain embodiments of the invention, useful organolithium compounds are methyl lithium, ethyl lithium, propyl lithium, n-butyl lithium, sec-butyl lithium, t- (Meth) acrylate, phenyl lithium, tolyl lithium, xylyl lithium, benzyl lithium, (dimethyl phenyl) methyl lithium, allyl lithium, or combinations thereof. In an embodiment, the organolithium compound is methyllithium, ethyllithium, propyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, or any combination thereof; Alternatively, it comprises, consists essentially of, or consists of phenyllithium, tolylithium, xylylithium, or any combination thereof. In some embodiments, the organolithium compound is methyllithium; Otherwise, ethyl lithium; Otherwise, propyl lithium; Otherwise, n-butyllithium; Alternatively, sec-butyllithium; Otherwise, t-butyllithium; Otherwise, neopentyl lithium; Otherwise, trimethylsilylmethyl lithium; Otherwise, phenyl lithium; Otherwise, tolylithium; Otherwise, xylyl lithium; Otherwise, benzyllithium; Alternatively, (dimethylphenyl) methyllithium; Or alternatively, comprise, consist essentially of, or consist of allyl lithium.

In certain embodiments described herein in one aspect and wherein the catalyst system employs an organolithium compound, the metal mole ratio of the organolithium compound to the metallocene is greater than 0.1: 1 (Li: the metal of the metallocene); Otherwise, greater than 1: 1; Alternatively, greater than 10: 1; Alternatively, may exceed 50: 1. In some embodiments where the catalyst system employs an organolithium compound, the metal mole ratio of organolithium compound to metallocene (Li: metal of metallocene) is from 0.1: 1 to 100,000: 1; Alternatively from 1: 1 to 10,000: 1; Alternatively from 10: 1 to 1,000: 1; Alternatively from 50: 1 to 500: 1. When the metallocene contains a specific metal (for example Zr), the ratio is Li: specific metal ratio (for example Li: Zr molar ratio).

Organic boron  compound

Another embodiment of the present invention provides an oligomerization process (or PAO process) comprising contacting a catalyst system comprising an alpha olefin monomer and a metallocene. In an embodiment, the catalyst system may further comprise an activator. In certain embodiments provided herein, the activator may comprise a solid oxide chemically treated with an electron attracting anion. In another embodiment of any of the embodiments provided herein, the catalyst system may comprise at least one organoboron compound, either in combination with the chemically-treated solid oxide and / or any other activator (s) or alone have. In some embodiments, the catalyst system comprises, consists essentially of, or consists of a metallocene, a first activator comprising a chemically-treated solid oxide, and a second activator comprising an organic boron compound.

In one embodiment, the organoboron compounds that can be used in the catalyst systems of the present invention are diverse. In one embodiment, the organoboron compound is a neutral boron compound, a borate salt, or a combination thereof; Alternatively, a neutral organoboron compound; Or alternatively, a borate. In one embodiment, the organoboron compound of the present invention is a fluorinated organic boron compound, a fluorinated organic borate salt compound, or a combination thereof; Alternatively, a fluorinated organoboron compound; Or alternatively, a fluorinated organic borate compound. Any fluorinated organic boron or fluorinated organic borate salt compound known in the art can be applied. The term fluorinated organic boron compounds has the usual meaning of referring to neutral compounds of the BY ₃ type. The term fluorinated organic borate compound also has the usual meaning of referring to monovalent anionic salts of fluorinated organic boron compounds in the form [cation] ⁺ [BY ₄ ] ^- , where Y is a fluorinated organic group. Conveniently, the fluorinated organic boron and fluorinated organic borate compounds are typically referred to as organic boron compounds, or their respective names, depending on the context.

In embodiments, the fluorinated organic borate compounds that may be used as activators in the present invention include, but are not limited to, fluorinated aryl borates such as N, N -dimethyl anilinium tetrakis- (pentafluorophenyl) (Pentafluorophenyl) borate, lithium tetrakis- (pentafluorophenyl) borate, N, N -dimethylanilinium tetrakis [3,5- Phenylcarbenium tetrakis [3,5-bis (trifluoromethyl) -phenyl] borate, and mixtures thereof; Alternatively, N, N -dimethyl anilinium tetrakis- (pentafluorophenyl) -borate; Alternatively, triphenylcarbenium tetrakis (pentafluorophenyl) borate; Alternatively, lithium tetrakis- (pentafluorophenyl) borate; Alternatively, N, N -dimethyl anilinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate; Or alternatively, triphenylcarbenium tetrakis [3,5-bis (trifluoromethyl) -phenyl] borate. Exemplary fluorinated organic boron compounds used as activators in the present invention include, but are not limited to, tris (pentafluorophenyl) boron, tris [3,5-bis (trifluoromethyl) -phenyl] boron, .

While not intending to be bound by the following theories, these fluorinated organic boronates and fluorinated organic boron compounds, and related compounds, are described in U. S. Patent No. 5,919, 983, which is incorporated herein by reference in its entirety, - coordination "anions.

In general, any amount of organoboron compound can be applied to the present invention. In one embodiment and in any of the embodiments described herein, the organoboron compound to metallocene molar ratio may be from 0.001: 1 to 100,000: 1. Alternatively and in certain embodiments, the organoboron compound to metallocene molar ratio is from 0.01: 1 to 10,000: 1; Alternatively 0.1: 1 to 100: 1; Alternatively 0.5: 1 to 10: 1; Alternatively from 0.2: 1 to 5: 1. Typically, the fluorinated organic boron or fluorinated organic borate compound content used as the metallocene activator is from 0.5 to 10 moles of organoboron compound per total moles of metallocene compound applied. In one embodiment, the fluorinated organic boron or fluorinated organic borate compound content used as the metallocene activator is from 0.8 mole to 5 moles of organoboron compound per total moles of metallocene compound applied.

Ionic ionic compound

Another aspect of the present invention provides an oligomerization process (or PAO process) comprising contacting a catalytic system comprising an alpha olefin monomer and a metallocene. In an embodiment, the catalyst system may further comprise an activator. In certain embodiments provided herein, the activator may comprise a solid oxide chemically treated with an electron attracting anion. In another embodiment of any of the embodiments provided herein, the catalyst system comprises at least one ionic ionic compound, either in combination with the chemically-treated solid oxide and / or any other activator (s) or alone . In some embodiments, the catalyst system comprises, consists essentially of, or consists of a metallocene, a first activator comprising a chemically-treated solid oxide, and a second activator comprising an ionic ionic compound. Exemplary ionic ionic compounds are described in U.S. Patent Nos. 5,576,259 and 5,807,938, each of which is incorporated herein by reference in its entirety.

Ionic ionic compounds are ionic compounds that improve catalyst system activity. Without being bound by theory, it is believed that the ionic ionic compound will react with the metallocene compound to convert it to a cationic or a metallocene compound which may be an initiating cation. Again, although not intending to be bound by theory, it is believed that ionic ionic compounds function as ionic compounds that at least partially extract an anionic ligand, a group II (non-η ⁵ -alkadiene) ligand capable of being released from the metallocene do. However, the ionic ionic compound may be used to ionize the metallocene, to extract the group II ligand to weaken the metal-II group ligand bond in the metallocene, or to simply ligate to the group II ligand, or It is an active agent regardless of other mechanisms that cause any activation.

 Also, the ionized ionic compound does not need to activate only the metallocene. The activation action of the ionized ionic compound is evident in the increased activity of the overall catalyst composition as compared to the catalyst composition containing the catalyst composition without any ionizing ionic compound. Nor does the ionic ionic compound need to activate the same metallocene to the same extent.

In one embodiment and in any of the embodiments described herein, the ionic ionic compound has the formula:

[Q] ⁺ [M ⁴ Z ₄ ] ^- .

In an embodiment, Q is selected from the group consisting of [NR ^A R ^B R ^C R ^D ] ⁺ , [CR ^E R ^F R ^G ] ⁺ , [C ₇ H ₇ ] ⁺ , Li ⁺ , Na ⁺ , or K ⁺ ; Otherwise, [NR ^A R ^B R ^C R ^D ] ⁺ ; Otherwise, [CR ^E R ^F R ^G ] ⁺ ; Alternatively, [C ₇ H ₇ ] ⁺ ; Alternatively, Li ⁺ , Na ⁺ , or K ⁺ ; Alternatively, Li ⁺ ; Unlike Na ⁺ ; Alternatively, it may be K ⁺ . In an embodiment, R ^A , R ^B , and R ^C are each independently hydrogen, and a C ₁ to C ₂₀ hydrocarbyl group; Alternatively, hydrogen and a C ₁ to C ₁₀ hydrocarbyl group; Alternatively, hydrogen and a C ₁ to C ₅ hydrocarbyl group; Alternatively, hydrogen and a C ₆ to C ₂₀ aryl group; Alternatively, hydrogen and a C ₆ to C ₁₅ aryl group; Alternatively, hydrogen and a C ₆ to C ₁₀ aryl group; Alternatively, hydrogen and a C ₁ to C ₂₀ alkyl group; Alternatively, hydrogen and a C ₁ to C ₁₀ alkyl group; Or alternatively, hydrogen and a C ₁ to C ₅ alkyl group; Otherwise, hydrogen; Alternatively, a C ₁ to C ₂₀ hydrocarbyl group; Alternatively, a C ₁ to C ₁₀ hydrocarbyl group; Alternatively, a C ₁ to C ₅ hydrocarbyl group; Alternatively, a C ₆ to C ₂₀ aryl group; Alternatively, a C ₆ to C ₁₅ aryl group; Alternatively, a C ₆ to C ₁₀ aryl group; Otherwise, a C ₁ to C ₂₀ alkyl group; Alternatively, a C ₁ to C ₁₀ alkyl group; Or alternatively may be a C ₁ to C ₅ alkyl group. In an embodiment, R ^D is hydrogen, a halide, and a C ₁ to C ₂₀ hydrocarbyl group; Alternatively, hydrogen, halide, and C ₁ to C ₁₀ hydrocarbyl groups; Alternatively, hydrogen, halide, and C ₁ to C ₅ hydrocarbyl groups; Alternatively, hydrogen, halide, and a C ₆ to C ₂₀ aryl group; Alternatively, hydrogen, halide, and a C ₆ to C ₁₅ aryl group; Alternatively, hydrogen, halide, and a C ₆ to C ₁₀ aryl group; Alternatively, hydrogen, halide, and a C ₁ to C ₂₀ alkyl group; Alternatively, hydrogen, halide, and a C ₁ to C ₁₀ alkyl group; Or alternatively, hydrogen, halide, and C ₁ to C ₅ alkyl; Otherwise, hydrogen; Otherwise, halide; Alternatively, and a C ₁ to C ₂₀ hydrocarbyl group; Alternatively, a C ₁ to C ₁₀ hydrocarbyl group; Alternatively, a C ₁ to C ₅ hydrocarbyl group; Alternatively, a C ₆ to C ₂₀ aryl group; Alternatively, a C ₆ to C ₁₅ aryl group; Alternatively, a C ₆ to C ₁₀ aryl group; Otherwise, a C ₁ to C ₂₀ alkyl group; Alternatively, a C ₁ to C ₁₀ alkyl group; Or alternatively may be selected from C ₁ to C ₅ alkyl groups. In an embodiment, R ^E , R ^F , and R ^G are each independently selected from the group consisting of hydrogen, halide, and C ₁ to C ₂₀ hydrocarbyl groups; Alternatively, hydrogen, halide, and C ₁ to C ₁₀ hydrocarbyl groups; Alternatively, hydrogen, halide, and C ₁ to C ₅ hydrocarbyl groups; Alternatively, hydrogen, halide, and a C ₆ to C ₂₀ aryl group; Alternatively, hydrogen, halide, and a C ₆ to C ₁₅ aryl group; Or alternatively, hydrogen, halide, and a C ₆ to C ₁₀ aryl group; Otherwise, hydrogen; Otherwise, halide; Alternatively, a C ₁ to C ₂₀ hydrocarbyl group; Alternatively, a C ₁ to C ₁₀ hydrocarbyl group; Alternatively, a C ₁ to C ₅ hydrocarbyl group; Alternatively, a C ₆ to C ₂₀ aryl group; Alternatively, a C ₆ to C ₁₅ aryl group; Or alternatively a C ₆ to C ₁₀ aryl group. Alkyl groups, aryl groups, and halides are independently described herein as potential groups for X ¹⁰ and X ¹¹ of an organoaluminum compound having the formula Al (X ¹⁰ ) _n (X ¹¹ ) _3-n , wherein these alkyl groups, The halide is not limited and can be used to describe ionic ionic compounds having the formula [NR ^A R ^B R ^C R ^D ] ⁺ or [CR ^E R ^F R ^G ] ⁺ used in the embodiments and embodiments described in the present invention Can be applied.

; 달리, 할라이드; 또는 달리,

일 수 있다. 실시예에서, X¹, X², X³, X⁴, 및 X⁵ 는 독립적으로 수소, 할라이드, C₁ 내지 C₂₀ 히드로카르빌기, 또는 C₁ 내지 C₂₀ 히드로카르복시드기 (히드로카르복시기라고도 칭함); 달리, 수소, 할라이드, C₁ 내지 C₁₀ 히드로카르빌기, 또는 C₁ 내지 C₁₀ 히드로카르복시드기; 달리, 수소, 할라이드, C₆ 내지 C₂₀ 아릴기, 또는 C₆ 내지 C₂₀ 아릴록시드기; 달리, 수소, 할라이드, C₆ 내지 C₁₀ 아릴기, 또는 C₆ 내지 C₁₀ 아릴록시드기; 달리, 수소, 할라이드, C₁ 내지 C₂₀ 알킬기, 또는 C₁ 내지 C₂₀ 알콕시드기 (알콕시기라고도 칭함); 달리, 수소, 할라이드, C₁ 내지 C₁₀ 알킬기, 또는 C₁ 내지 C₁₀ 알콕시드기; 또는 달리, 수소, 할라이드, C₁ 내지 C₅ 알킬기, 또는 C₁ 내지 C₅ 알콕시드기일 수 있다. 알킬기, 아릴기, 알콕시드기, 아릴록시드기, 및 할라이드는 식 Al(X¹⁰)_n(X¹¹)_3-n 을 가지는 유기알루미늄 화합물의 X¹⁰ 및 X¹¹ 에 대한 잠재적 기로 독립적으로 본원에 기재되며 이들 알킬기, 아릴기, 알콕시드기, 아릴록시드기, 및 할라이드는 제한되지 않고 X¹, X², X³, X⁴, 및 X⁵로 적용될 수 있다_. 일부 실시예들에서,

; 는 페닐, p-톨릴, m-톨릴, 2,4-디메틸페닐, 3,5-디메틸페닐, 펜타플루오로페닐, 및 3,5-비스(트리플루오로메틸)페닐; 달리, 페닐; 달리, p-톨릴; 달리, m-톨릴; 달리, 2,4-디메틸페닐; 달리, 3,5-디메틸페닐; 달리, 펜타플루오로페닐; 또는 달리, 3,5-비스(트리플루오로메틸)페닐일 수 있다. In some embodiments, Q is trialkylammonium or dialkylarylammonium (e.g., dimethylanilinium); Alternatively, triphenylcarbenium or substituted triphenylcarbenium; Otherwise, tropium or substituted tropiium; Alternatively, trialkylammonium; Alternatively, unlike dialkylarylammonium (e.g., dimethylanilinium), triphenylcarbenium; Or, alternatively, tropielium. In another embodiment, Q is selected from the group consisting of e tri (n-butyl) ammonium, N, N - dimethylanilinium, triphenylcarbenium, tropium, lithium, sodium, and potassium; Alternatively, tri (n-butyl) ammonium and N, N - dimethylanilinium; Alternatively, triphenylcarbenium, tropiium; Alternatively, it may be lithium, sodium and potassium. In an embodiment, M ⁴ is B or Al; Otherwise, B; Alternatively, it can be Al. In an embodiment, Z is halide or

; Otherwise, halide; Alternatively,

Lt; / RTI &gt; In an embodiment, X ¹ , X ² , X ³ , X ⁴ , and X ⁵ are independently hydrogen, a halide, a C ₁ to C ₂₀ hydrocarbyl group, or a C ₁ to C ₂₀ hydrocarbyl group (also referred to as a hydrocarboxy group) ; Alternatively, hydrogen, halide, C ₁ to C ₁₀ hydrocarbyl group, or C ₁ to C ₁₀ hydrocarbyl group; Alternatively, hydrogen, a halide, a C ₆ to C ₂₀ aryl group, or a C ₆ to C ₂₀ aryloxyd group; Alternatively, hydrogen, halide, C ₆ to C ₁₀ aryl group, or C ₆ to C ₁₀ aryloxyd group; Alternatively, hydrogen, halide, C ₁ to C ₂₀ alkyl group, or C ₁ to C ₂₀ alkoxy group (also referred to as alkoxy group); Alternatively, hydrogen, a halide, a C ₁ to C ₁₀ alkyl group, or a C ₁ to C ₁₀ alkoxy group; Or alternatively may be hydrogen, halide, a C ₁ to C ₅ alkyl group, or a C ₁ to C ₅ alkoxide group. The alkyl group, aryl group, alkoxide group, aryloxid group, and halide are independently referred to herein as a potential group for X ¹⁰ and X ¹¹ of an organoaluminum compound having the formula Al (X ¹⁰ ) _n (X ¹¹ ) _3-n The alkyl group, aryl group, alkoxide group, aryloxid group, and halide may be applied without limitation to X ¹ , X ² , X ³ , X ⁴ , and X ⁵ _. In some embodiments,

; Is phenyl, p-tolyl, m-tolyl, 2,4-dimethylphenyl, 3,5-dimethylphenyl, pentafluorophenyl, and 3,5-bis (trifluoromethyl) phenyl; Otherwise, phenyl; Otherwise, p-tolyl; Otherwise, m-tolyl; Alternatively, 2,4-dimethylphenyl; Otherwise, 3,5-dimethylphenyl; Alternatively, pentafluorophenyl; Or alternatively, 3,5-bis (trifluoromethyl) phenyl.

Exemplary ionic ionic compounds include, but are not limited to, tri (n-butyl) ammonium tetrakis (p-tolyl) borate, tri (n-butyl) -ammonium tetrakis , Tri (n-butyl) ammonium tetrakis (2,4-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (Pentafluorophenyl) borate, N, N - dimethylanilinium tetrakis (p-tolyl) borate, N (trimethylsilyl) , N-dimethylanilinium tetrakis (m- tolyl) borate, N, N-dimethylanilinium tetrakis (2,4-dimethylphenyl) borate, N, N-dimethylanilinium tetrakis (3, 5-dimethyl- phenyl) borate, N, N - dimethylanilinium tetrakis [3,5- bis (trifluoromethyl) phenyl] borate, or N, N - dimethylanilinium tetrakis (pen Fluorophenyl) borate; Alternatively, triphenylcarbenium tetrakis (p-tolyl) borate, triphenylcarbenium tetrakis (m-tolyl) borate, triphenylcarbenium tetrakis (2,4- (3,5-dimethylphenyl) borate, triphenylcarbenium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, or triphenylcarbenium tetrakis (pentafluorophenyl) borate; Alternatively, tributyl tetrakis (p-tolyl) borate, tropium tetrakis (m-tolyl) borate, tropium tetrakis (2,4-dimethylphenyl) Borate, tropiium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, or tropium tetrakis (pentafluorophenyl) borate; Alternatively, lithium tetrakis (pentafluorophenyl) borate, lithium tetrakis (phenyl) borate, lithium tetrakis (ptolyl) borate, lithium tetrakis (m- Dimethylphenyl) borate, lithium tetrakis- (3,5-dimethylphenyl) borate, or lithium tetrafluoroborate; Alternatively, it is possible to use sodium tetrakis (pentafluorophenyl) borate, sodium tetrakis (phenyl) borate, sodium tetrakis (p-tolyl) borate, sodium tetrakis Phenyl) borate, sodium tetrakis- (3,5-dimethylphenyl) borate, or sodium tetrafluoroborate; Alternatively, potassium tetrakis (pentafluorophenyl) borate, potassium tetrakis (phenyl) borate, potassium tetrakis (p-tolyl) borate, potassium tetrakis (m- Dimethyl-phenyl) borate, potassium tetrakis (3,5-dimethylphenyl) borate, or potassium tetrafluoroborate; Alternatively, tri (n-butyl) ammonium tetrakis (p-tolyl) aluminate, tri (n-butyl) ammonium tetrakis Dimethylphenyl) aluminate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) -aluminate, tri (n-butyl) N, N-dimethylanilinium tetrakis (p- tolyl) - aluminate, N, N-dimethylanilinium tetrakis (m- tolyl) aluminate, N, N- dimethylanilinium tetrakis (2,4 (Dimethylphenyl) aluminate, N, N - dimethylanilinium tetrakis (3,5-dimethylphenyl) aluminate, or N, N - dimethylanilinium tetrakis ; Alternatively, there may be mentioned triphenylcarbenium tetrakis (p-tolyl) aluminate, triphenylcarbenium tetrakis (m-tolyl) -aluminate, triphenylcarbenium tetrakis (2,4- Triphenyl-carbenium tetrakis (3,5-dimethylphenyl) aluminate, or triphenylcarbenium tetrakis- (pentafluorophenyl) aluminate; Alternatively, there may be mentioned tropiium tetrakis (p-tolyl) aluminate, tropium tetrakis (m-tolyl) aluminate, tropium tetrakis (2,4-dimethylphenyl) aluminate, tropium tetrakis , 5-dimethylphenyl) aluminate, or tropium tetrakis (pentafluorophenyl) aluminate; Alternatively, lithium tetrakis (pentafluorophenyl) aluminate, lithium tetrakis (phenyl) aluminate, lithium tetrakis (p-tolyl) aluminate, lithium tetrakis , Lithium tetrakis (2,4-dimethylphenyl) aluminate, lithium tetrakis (3,5-dimethylphenyl) aluminate, or lithium tetrafluoroborate; Alternatively, there may be mentioned sodium tetrakis (pentafluorophenyl) aluminate, sodium tetrakis (phenyl) aluminate, sodium tetrakis (p-tolyl) -aluminate, sodium tetrakis Sodium tetrakis (2,4-dimethylphenyl) -aluminate, sodium tetrakis (3,5-dimethylphenyl) aluminate, or sodium tetrafluoride-aluminate; Or alternatively, potassium tetrakis (p-tolyl) aluminate, potassium tetrakis (pentafluorophenyl) aluminate, potassium tetrakis- (phenyl) aluminate, potassium tetrakis Potassium tetrakis (2,4-dimethylphenyl) aluminate, potassium tetrakis (3,5-dimethylphenyl) aluminate, potassium tetrafluoroaluminate. In some embodiments, the ionic ionic compound is selected from the group consisting of tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) borate, tri (n-butyl) -ammonium tetrakis [3,5- N, N - dimethylanilinium tetrakis (p-tolyl) borate, N, N - dimethylanilinium tetrakis m (methyl) phenylborate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) -tolyl) borate, N, N-dimethylanilinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenyl - (3, 4-dimethylphenyl) borate, triphenylcarbenium tetrakis (p-tolyl) borate, triphenylcarbenium tetrakis (m-tolyl) borate, triphenylcarbenium tetrakis 5-dimethylphenyl) borate, triphenylcarbenium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, (4,5-dimethylphenyl) aluminate, lithium tetrakis (p-tolyl) aluminate, lithium tetrakis (m-tolyl) aluminate, lithium tetrakis ) Aluminate salt.

In other and some embodiments, the ionic ionic compound is selected from the group consisting of tri (n-butyl) -ammonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, tri (n-butyl) ammonium tetrakis N, N - dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenyl (triphenylphosphine) borate, N, N - dimethylanilinium tetrakis [3,5- Carbenium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, lithium tetrakis (p-tolyl) aluminate, or lithium tetrakis (m-tolyl) aluminate; Alternatively, tri (n-butyl) -ammonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate; Alternatively, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate; Alternatively, N, N - dimethyl anilinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate; Alternatively, N, N - dimethyl anilinium tetrakis (pentafluorophenyl) borate; Alternatively, triphenylcarbenium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate; Alternatively, lithium tetrakis (p-tolyl) aluminate; Alternatively, it may be lithium tetrakis (m-tolyl) aluminate. In another embodiment, the ionic compound may be any combination of ionic compounds mentioned herein. However, the ionic ionic compound is not limited in the present invention.

In one embodiment and in any of the embodiments described herein, the ionic ionic compound to metallocene molar ratio may be from 0.001: 1 to 100,000: 1. Alternatively, in certain embodiments or embodiments, the ionic ion compound to metallocene molar ratio is from 0.01: 1 to 10,000: 1; Alternatively 0.1: 1 to 100: 1; Alternatively 0.5: 1 to 10: 1; Alternatively from 0.2: 1 to 5: 1.

Catalyst System Manufacturing

In an embodiment and in certain embodiments of the present invention, the catalyst system comprises a metallocene and at least one chemically-treated solid oxide; Alternatively, the catalyst system comprises, consists essentially of, or consists of a metallocene and at least one aluminoxane. In an embodiment, the catalyst system comprises, consists essentially of, or consists of a metallocene, a first activator, and a second activator. Activators are provided herein and may be applied without limitation to the activator of the catalyst systems described herein. In one embodiment and in any of the embodiments described herein, the catalyst system comprises a first activator comprising a metallocene, at least one chemically-treated solid oxide, (or substantially consisting of or consisting of) (Or substantially consists of, or consists of) a second activator. Other activators such as at least one organoaluminum compound may also be used in the catalyst system. In another aspect, the present invention encompasses a method of making a catalyst system. In general, the catalyst system can be obtained by contacting the catalyst system components in any order or order.

In other and optional embodiments of the present invention, the metallocene compound is pre-contacted with the olefinic monomer, which is not necessarily an oligomerized alpha olefin monomer, and the organoaluminum compound during the first period of time, and such pre- Lt; RTI ID = 0.0 &gt; solid oxide. In one embodiment, the contact first time between the metallocene compound or compounds, the olefinic monomer, and the organoaluminum compound, the pre-contact time is typically from 0.1 to 24 hours; Alternatively 0.1 to 1 hour; Alternatively from 10 minutes to 30 minutes.

In another embodiment of the present invention, the pre-contact mixture of the first, second, or both metallocene compounds, the olefinic monomer, and the organoaluminum compound may then be contacted with the chemically treated solid oxide. A composition further comprising a chemically treated solid oxide is referred to as a postcontact mixture. Typically, the postcontact mixture optionally retains the contact during the contact second phase, post-contact time, after which the oligomerization process is initiated. In one embodiment, the post contact time between the pre-contact mixture and the chemically treated solid oxide can range from 0.1 hour to 24 hours. In other embodiments, the post contact time can be from 0.1 hour to 1 hour.

In one embodiment, pre-contact, post-contact, or both steps can improve oligomerization productivity as compared to the same catalyst system lacking pre- or post-contact. However, in the present invention, either the pre-contacting step or the post-contacting step may not be necessary.

When the organoaluminum compound is applied in combination with the chemically treated solid oxide, the postcontact mixture is maintained at a temperature sufficient to allow adsorption, impregnation, or interaction of the precontacted mixture and the chemically treated solid oxide, And adsorbed or deposited. For example, the postcontact mixture may be heated to a temperature of 0 ° C to 150 ° C; Or alternatively, from 40 캜 to 95 캜.

When an organoaluminum compound is used as the activator (first, second, or the like), the metal mole ratio of the aluminum to the metallocene of the organoaluminum activator (sometimes referred to as the metal of Al: metallocene) have. In one embodiment, the total molar amount of metal in the aluminum-to-metallocene compound in the organoaluminum compound, that is, the molar ratio of the total moles of all metallocene compounds when one or more metallocenes are applied is greater than 0.1: 1; Otherwise, greater than 1: 1; Alternatively, greater than 10: 1; Alternatively, may exceed 50: 1. In some embodiments, the molar ratio of aluminum in the organoaluminum compound to the total moles of metal in the metallocene compound is from 0.1: 1 to 100,000: 1; Alternatively from 1: 1 to 10,000: 1; Alternatively from 10: 1 to 1,000: 1; Alternatively from 50: 1 to 500: 1. When a metallocene contains a specific metal (such as Zr), it is referred to as the molar ratio of aluminum to the specific metal of the organoaluminum activator (e.g., Al: Zr mole ratio if a zirconium metallocene is used). These molar ratios reflect the molar ratio of the total moles of metal in the aluminum to the metallocene compound (s) of the organoaluminum activator when both the pre-contact mixture and the post-contact mixture are combined.

When the pre-contacting step is applied, generally the molar ratio of total olefin monomer to metallocene combined in the pre-contact mixture is from 1:10 to 100,000: 1; Alternatively, from 10: 1 to 1,000: 1.

In another aspect of the invention, when the organoaluminum compound is combined with the chemically treated solid oxide, the weight ratio of chemically treated solid oxide to organoaluminum compound may be from 1: 5 to 1,000: 1. In other embodiments, the chemically treated solid oxide to organoaluminum compound weight ratio can be from 1: 3 to 100: 1, and in yet another embodiment from 1: 1 to 50: 1.

In another aspect of the invention, the weight ratio of chemically treated solid oxide to total metallocene compounds applied is less than 1,000,000: 1; Otherwise, less than 100,000: 1; Otherwise, less than 10,000: 1; Alternatively, less than 5,000: 1. In some embodiments, the weight ratio of chemically treated solid oxide to total metallocene compounds applied is from 1: 1 to 100,000: 1; Alternatively from 10: 1 to 10,000: 1; Alternatively from 50: 1 to 5,000: 1; Alternatively, may range from 100: 1 to 1,000: 1.

In one aspect of the present invention that utilizes a chemically treated solid oxide, aluminoxane is not necessarily required to form the catalyst system described herein, and this feature can lower the cost of oligomer production. Thus, in one embodiment, an oligomerization process (or PAO production process) comprising an alpha olefin monomer and a catalyst system contacting step can utilize a catalyst system substantially free of additional alumoxane. In one embodiment and in certain embodiments of the present invention, the catalyst system can employ chemically treated solid oxides substantially free of trialkylaluminum compounds and additional aluminoxane.

In addition, when using chemically treated solid oxides, it is not necessary to necessarily include the expensive borate compound or MgCl ₂ in the catalyst system. However, an aluminoxane, an organoboron compound, an ionic compound ion, if necessary, an organic zinc compound, MgC1 _2, waters or any combination thereof may be used in the catalyst system. In addition, in one embodiment, the activating agent, such as aluminoxane, organoboron compound, ionic ionic compound, organozinc compound, or any combination thereof, is present in the presence or absence of a chemically treated solid oxide; Alternatively, it can be used as an activator with the metallocene in the presence or absence of an organoaluminum compound.

In one aspect, the activity of the catalyst system described herein is greater than 10 grams of olefin oligomer / metallocene gram (?); Alternatively, 100 grams of olefin oligomer / metallocene or greater; Alternatively, 1,000 grams of olefin oligomer / metallocene grams or more; Alternatively, 5,000 grams of olefin oligomer / metallocene grams or more; Otherwise, 10,000 grams of olefin oligomer / metallocene or greater; Alternatively, 25,000 grams of olefin oligomer / metallocene grams or more; Alternatively, 50,000 grams of olefin oligomer / metallocene or greater; Alternatively, 75,000 grams of olefin oligomer / metallocene grams or more; Alternatively, it may be greater than or equal to 100,000 grams of olefin oligomer / metallocene gram. In an embodiment, the activity of the catalyst system described herein is greater than 1,000 grams of olefin oligomer / metallocene grams to 1,000,000,000 grams of olefin oligomer / metallocene grams, 5,000 grams of olefin oligomer / metallocene grams to 750,000,000 grams of olefin Oligomers / metallocenes; Alternatively, 10,000 grams of olefinic oligomers / metallocenes to 500,000,000 grams of olefinic oligomers / metallocenes; Alternatively, 25,000 grams of olefinic oligomers / metallocenes to 250,000,000 grams of olefinic oligomers / metallocenes; Alternatively, 50,000 grams of olefin oligomer / metallocene grams to 100,000,000 grams of olefin oligomer / metallocene grams; Alternatively, 75,000 grams of olefinic oligomers / metallocenes to 50,000,000 grams of olefinic oligomers / metallocenes; Alternatively, it may range from 100,000 grams of olefin oligomer / metallocene grams to 10,000,000 grams of olefin oligomer / metallocene grams.

In one aspect, the catalytic activity of the catalyst of the present invention can typically be greater than or equal to 0.1 grams olefin oligomer per gram of chemically treated solid oxide per hour (abbreviation g oligomer / g CTSO · hr) (≥). The catalytic activity is measured under the olefin oligomerization conditions employed. Any reactor used in this measurement should be substantially free of any wall foreign matter, coating or other contaminant forms when measured. In another embodiment, the catalyst of the present invention has an activity of at least 0.5 g oligomer / g CTSO · hr as measured under the conditions mentioned; Otherwise, 0.7 g oligomer / g CTSO · hr or more; Otherwise, 1 g oligomer / g CTSO · hr or more; Otherwise, 1.5 g oligomer / g CTSO · hr or more; Otherwise, 2 g oligomer / g CTSO · hr or more; Otherwise, 2.5 g oligomer / g CTSO · hr or more; Otherwise, 5 g oligomer / g CTSO · hr or more; Otherwise, 10 g oligomer / g CTSO · hr or more; Otherwise, 20 g oligomer / g CTSO · hr or more; Otherwise, 50 g oligomer / g CTSO · hr or more; Otherwise, 100 g oligomer / g CTSO · hr or more; Otherwise, 200 g oligomer / g CTSO · hr or more; Otherwise, 500 g oligomer / g CTSO · hr or more; Alternatively, it may be at least 1000 g oligomer / g CTSO · hr. In another embodiment, the catalyst system of the present invention has an activity of from 0.1 g oligomer / g CTSO · hr to 5000 g oligomer / g CTSO · hr, Otherwise, 0.25 g oligomer / g CTSO · hr to 2,500 g oligomer / g CTSO · hr; Otherwise, 0.5 g oligomer / g CTSO · hr to 1,000 g oligomer / g CTSO · hr; Alternatively, 0.75 g oligomer / g CTSO · hr to 750 g oligomer / g CTSO · hr; Alternatively, 1 g oligomer / g CTSO · hr to 500 g oligomer / g CTSO · hr; Alternatively, it may range from 5 g oligomer / g CTSO · hr to 250 g oligomer / g CTSO · hr.

Oligomerization  fair

The olefin oligomerization according to the present invention may be carried out by any method known in the art suitable for the particular alpha olefin monomer (s) to be applied in the oligomerization process. For example, oligomerization processes include, but are not limited to, slurry oligomerization, solution oligomerization, and the like, and multi-reactor combinations thereof. For example, a stirred reactor may be applied to the batch process, and the reaction may proceed continuously in a loop reactor or a continuous stirred reactor. Slurry oligomerization processes (also known as particle formation processes) are disclosed in U.S. Patent No. 3,248,179, which is known in the art and is incorporated herein by reference in its entirety. Other oligomerization methods of the present invention for the slurry process of the present invention use a loop reactor of the type disclosed in U.S. Patent No. 3,248,179, which is incorporated herein by reference in its entirety, and may be used in series, in parallel, Is to use a plurality of stirred reactors with different reaction conditions.

In one embodiment, the alpha olefin oligomerization process of the present invention comprises contacting at least one alpha olefin monomer and catalyst system for oligomer product formation. Depending on the oligomerization process, the oligomerization reactor effluent in the reactor has an oligomer product and typically some residual monomers (along with other components such as catalyst systems or catalyst system components) Some volatile components are removed from the effluent to provide a heavy oligomer product. The heavy oligomer product undergoes hydrogenation to form polyalphaolefin (PAO). In some non-limiting embodiments, the reactor effluent may be treated with an auxiliary (deactivator) that deactivates the system prior to separation. In a non-limiting embodiment, the deactivating agent is water, an alcohol, or any combination thereof; Otherwise, water; Or otherwise comprise, consist essentially of, or consist of alcohol.

Some suitable and / or preferred oligomerization conditions, catalyst components, contact sequences, monomers are provided herein and oligomer products, heavy oligomer products, and some PAO features are further described. These embodiments are not limiting, but rather illustrate how the selection of candidate catalyst components and reaction conditions and the properties of the resulting products are specified.

In one aspect, the invention relates to an oligomerization process comprising: a) contacting a catalyst system comprising an alpha olefin monomer, and a metallocene; and b) forming an oligomer product under oligomerization conditions. In another aspect, the present invention relates to an oligomerization process comprising: a) contacting a catalyst system comprising an alpha olefin monomer and a metallocene; b) forming an oligomer product under oligomerization conditions; and c) And an oligomerization reactor effluent separation step comprising an oligomer product to provide the product. In another aspect, the present invention relates to an oligomerization process comprising: a) contacting a catalyst system comprising an alpha olefin monomer and a metallocene; b) forming an oligomer product under oligomerization conditions; c) , And d) hydrogenating the heavy oligomer product to provide the polyalphaolefin. &Lt; Desc / Clms Page number 7 &gt; In another aspect, the present invention relates to a process for producing polyalphaolefins comprising: a) contacting a catalyst system comprising an alpha olefin monomer and a metallocene; b) forming an oligomer product under oligomerization conditions; c) An oligomerization reactor effluent separation step comprising an oligomer product to provide a product of a heavy oligomer, and d) a hydrogenation step of a heavy oligomer product to provide a polyalphaolefin. Generally, it is preferred to use an olefinic monomer, an alpha olefin monomer, a catalyst system, catalyst system components (e.g. metallocene, activator, and other components), solvent (if used), oligomer product, oligomerization conditions, The oligomer product, hydrogenation conditions, and / or polyalphaolefins are independent components of the oligomerization process and / or polyalphaolefin production process described herein. These features are described herein independently and the oligomerization process (s) and / or polyalphaolefin production process (s) can be carried out using the alpha olefin monomers described herein, the catalyst systems described herein, the catalyst system components described herein (If used), the oligomer product described herein, the oligomerization conditions described herein, the reactor effluent described herein, the heavy oligomer product described herein, the oligomer product described herein Described hydrogenation conditions, and / or any combinations of the polyalphaolefins described herein. In an embodiment, the oligomer product can be recovered. In some embodiments, the heavy oligomer product can be recovered. In another embodiment, the hydrogenated heavy oligomer product can be recovered. In still other embodiments, polyalpha olefins may be recovered.

In a non-limiting embodiment, the alpha olefin monomer used in the oligomerization process (s) or polyalphaolefin production process (s) comprises or consists essentially of a C ₆ to C ₁₆ normal alpha olefin; Alternatively, C ₆ normal alpha olefins, C ₈ normal alpha olefins, C ₁₀ normal alpha olefins, C ₁₂ normal alpha olefins, C ₁₄ normal alpha olefins, or any combination thereof; Or alternatively consists essentially of, or consists of C ₈ normal alpha olefins, C ₁₀ normal alpha olefins, C ₁₂ normal alpha olefins, or any combination thereof. In some non-limiting embodiments, the alpha olefin monomers used in the oligomerization process (s) or polyalphaolefin production method (s) include C ₆ normal alpha olefins; Alternatively, C ₈ normal alpha olefins; Alternatively, C ₁₀ normal alpha olefins; Alternatively, C ₁₂ normal alpha olefins; Or alternatively consists essentially of, or consists of C ₁₄ normal alpha olefins. Other alpha olefin monomers are described herein and may be used in the disclosed process without limitation.

In a non-limiting embodiment, the catalyst system used in the oligomerization process (s) or the polyalphaolefin production process (s) comprises a metallocene and an activator; Alternatively, the metallocene, the first activator, and the second activator are comprised, substantially or consist of. Generally, metallocenes and activators are independent catalyst system components. These catalyst system features can be independently applied in any combination as described herein and in describing the catalyst system. These independent combinations can again be applied to any olefin oligomerization method (s) described herein and / or to the polyalphaolefin production method (s) described herein. According to another aspect, the catalyst system comprises, consists essentially of, or consists of a metallocene, a first activator comprising a chemically-treated solid oxide, and a second activator. In another embodiment, the catalyst system applied to the oligomerization process (s) or polyalphaolefin production process (s) comprises a metallocene, a first activator comprising a chemically-treated solid oxide, and an organoaluminum compound Or a second activator. Other catalyst systems, and / or catalyst system components may be applied without limitation to the methods described and described herein.

In a non-limiting embodiment, the chemically-treated solid oxide, which is the first activator applied to the catalyst system used in the oligomerization process (s) or polyalphaolefin production process (s), is fluorinated alumina, chlorinated alumina, , Fluorinated silica-alumina, or any combination thereof. In a non-limiting example, the chemically-treated solid oxide, which is the first activator applied to the catalyst system used in the oligomerization process (s) or polyalphaolefin production process (s), is selected from fluorinated alumina, chlorinated alumina, Alumina, fluorinated silica-alumina, and any combination thereof; Otherwise, fluorinated alumina; Otherwise, chlorinated alumina; Otherwise, sulfated alumina; Alternatively, fluorinated silica-alumina is included, substantially made, or made. Other chemically-treated solid oxides can be applied without limitation to the methods described and described herein.

In a non-limiting embodiment, the oligomerization method (s) or polyalphaolefin generation method (s) an organoaluminum compound the second activator is formula Al (X ¹⁰⁾ that is applied to the catalyst system used in the _n (X ¹¹⁾ ₃ comprises, consists essentially of, or _consists of an organoaluminum compound having _-n ; Or otherwise comprise, consist essentially of, or consist of alumoxane. In some non-limiting embodiments, each X ¹⁰ of the organoaluminum compound having the formula Al (X ¹⁰ ) _n (X ¹¹ ) _{3 - n} may independently be a C ₁ to C ₂₀ hydrocarbyl. Other non-in-limiting embodiment, the formula _{^{Al (X 10) n (X}} 11) 3 - , each of X ¹¹ of the organoaluminum compound having _n are independently selected from halide, hydride, or C ₁ to C ₂₀ hydrocarbyl carboxy deuil . Some non-limiting examples in the formula Al (X ¹⁰⁾ _n (X ¹¹⁾ _3-n of the organoaluminum compound having _n may be of 1 to 3 days. In other non-limiting embodiments, the organoaluminum compound second activator applied to the catalyst system used in the oligomerization process (s) or the polyalphaolefin production process (s) is selected from the group consisting of trialkylaluminum; Alternatively, triisobutylaluminum is included, substantially or consisted of triisobutylaluminum. Other organoaluminum compounds may be applied without limitation to the methods described and described herein.

,

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,

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을 가지는 메탈로센, 또는 이들의 임의 조합; 달리, In a non-limiting embodiment, the metallocenes used in the oligomerization process (s) or polyalphaolefin production process (s)

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Or a combination thereof; Otherwise,

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; Otherwise,

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Or may be made substantially. In another non-limiting embodiment, the metallocenes used in the oligomerization process (s) or polyalphaolefin production process (s)

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; 달리,

; 또는 달리,

을 포함하거나, 실질적으로 이루어지거나, 이루어진다. 일부 비-제한적 실시예들에서, 각각의 R²⁰, R²¹, R²³, 및 R²⁴ 은 독립적으로 수소, C₁ 내지 C₂₀ 알킬기, 또는 C₁ 내지 C₂₀ 알케닐기; 달리, 수소; 달리, C₁ 내지 C₂₀ 알킬기; 또는 달리, C₁ 내지 C₂₀ 알케닐기일 수 있다. 일부 비-제한적 실시예들에서, 각각의 X¹², X¹³, X¹⁵, 및 X¹⁶ 은 독립적으로 F, Cl, Br, 또는 I; 달리, Cl 또는 Br; 달리, F; 달리, Cl; 달리, 또는 달리, I일 수 있다. 일부 비-제한적 실시예들에서, 올리고머화 방법(들) 또는 폴리알파올레핀 생성 방법(들)에서 사용되는 메탈로센은 식

,

,

,

,

,

,

,

,

,

을 가지는 메탈로센,

,

,

, Or any combination thereof; Otherwise,

; Otherwise,

; Otherwise,

; Alternatively,

Or may be made substantially. In some non-limiting embodiments, each of R ²⁰ , R ²¹ , R ²³ , and R ²⁴ is independently hydrogen, a C ₁ to C ₂₀ alkyl group, or a C ₁ to C ₂₀ alkenyl group; Otherwise, hydrogen; Otherwise, a C ₁ to C ₂₀ alkyl group; Or alternatively, a C ₁ to C ₂₀ alkenyl group. In some non-limiting embodiments, each of X ¹² , X ¹³ , X ¹⁵ , and X ¹⁶ is independently F, Cl, Br, or I; Alternatively Cl or Br; Otherwise, F; Otherwise, Cl; Otherwise, or otherwise, I. In some non-limiting embodiments, the metallocenes used in the oligomerization process (s) or polyalphaolefin production process (s)

,

,

,

,

,

,

,

,

,

&Lt; / RTI &gt;

,

,

,

, 또는 이들의 임의 조합; 달리,

,

,

, 또는 이들의 임의 조합; 달리,

,

,

, 또는 이들의 임의 조합; 달리,

,

, 또는 이들의 임의 조합; 달리,

; 달리,

; 달리,

; 달리,

; 달리,

; 달리,

; 달리,

; 달리,

; 달리,

; 또는 달리,

을 포함하거나, 실질적으로 이루어지거나, 이루어진다. Or any combination thereof; Otherwise,

,

,

,

, Or any combination thereof; Otherwise,

,

,

, Or any combination thereof; Otherwise,

,

,

, Or any combination thereof; Otherwise,

,

, Or any combination thereof; Otherwise,

; Otherwise,

; Otherwise,

; Otherwise,

; Otherwise,

; Otherwise,

; Otherwise,

; Otherwise,

; Otherwise,

; Alternatively,

Or may be made substantially.

In a non-limiting embodiment where the catalyst system employs a metallocene, a first activator, and a second activator, the oligomerization process (s) or polyalphaolefin production process (s) contact the alpha olefin monomer in any order . In some non-limiting embodiments, the alpha olefin monomer and the catalyst system comprise (1) an alpha olefin monomer and a second activator contact to form a first mixture, (2) a first mixture to form a second mixture, and A first activator contact, and (3) a second mixture and metallocene contact steps. In other non-limiting embodiments, the alpha olefin monomer and the catalyst system may comprise (1) an alpha olefin monomer and a second activator contact to form a mixture, and (2) a first activator and a metallocene and mixture simultaneous contact / RTI &gt; In other non-limiting embodiments, the alpha olefin monomer and the catalyst system may be contacted with the alpha olefin monomer, the metallocene, the first activator, and the second activator in a simultaneous contacting step.

In a non-limiting embodiment, the alpha olefin monomer to metallocene molar ratio in the oligomerization process (s) or polyalphaolefin production process (s) is greater than 100: 1; Otherwise, greater than 1,000: 1; Otherwise, greater than 10,000: 1; Alternatively, greater than 50,000: 1. In another non-limiting embodiment, the alpha olefin monomer to metallocene molar ratio in the oligomerization process (s) or polyalphaolefin production process (s) is from 100: 1 to 1,000,000,000; Alternatively 1,000: 1 to 100,000,000; Otherwise, 10,000: 1 to 10,000, 000; Alternatively, in the range of 50,000: 1 to 5,000,000. Other ratios of alpha olefin monomer to metallocene can be applied without limitation to the methods described and described herein.

In a non-limiting embodiment, the weight ratio of chemically-treated solid oxide to metallocene metal (e.g., zirconium metallocene to Zr) in the oligomerization process (s) or polyalphaolefin production process (s) under; Otherwise, less than 100,000: 1; Otherwise, less than 10,000: 1; Alternatively, less than 5,000: 1. In another non-limiting embodiment, the weight ratio of chemically-treated solid oxide to metallocene metal (such as zirconium metallocene to Zr) in the oligomerization process (s) or polyalphaolefin production process (s) : 1 to 100,000: 1; Alternatively from 10: 1 to 10,000: 1; Alternatively from 50: 1 to 5,000: 1; Alternatively, may range from 100: 1 to 1,000: 1. Other chemically-treated solid oxide to metallocene ratios can be applied without limitation to the methods described and described herein.

In a non-limiting embodiment, the molar ratio of the second activator aluminum to the metallocene metal (e.g., zirconium metallocene to Zr) in the oligomerization process (s) or polyalphaolefin production process (s) ; Otherwise, greater than 1: 1; Otherwise, greater than 10: 1; Alternatively, may exceed 50: 1. In a non-limiting embodiment, the molar ratio of the second activator aluminum to the metallocene metal (e.g., zirconium metallocene to Zr) in the oligomerization process (s) or polyalphaolefin production process (s) 100,000: 1; Alternatively from 1: 1 to 10,000: 1; Alternatively from 10: 1 to 1,000: 1; Alternatively from 50: 1 to 500: 1. Other aluminum to metallocene metal ratios may be applied without limitation to the methods described and described herein.

In a non-limiting embodiment, the molar ratio of aluminum-alkyl bond to metallocene metal (e.g., Zr in zirconium metallocene) in the second activator in the oligomerization process (s) or polyalphaolefin generation method (s) Is greater than 0.1: 1; Otherwise, greater than 0.2: 1; Otherwise, greater than 1: 1; Otherwise, greater than 5: 1; Otherwise, greater than 10: 1; Otherwise, greater than 50: 1; Otherwise, greater than 100: 1; Otherwise, greater than 150: 1; Alternatively, greater than 200: 1. In a non-limiting embodiment, the molar ratio of aluminum-alkyl bond to metallocene metal (e.g., Zr in zirconium metallocene) in the second activator in the oligomerization process (s) or polyalphaolefin generation method (s) Is from 0.1: 1 to 300,000: 1; Alternatively from 1: 1 to 100,000: 1; Alternatively from 10: 1 to 10,000: 1; Alternatively from 20: 1 to 5,000: 1; Alternatively, from 50: 1 to 1,000: 1. Other aluminum-alkyl bond to metallocene metal ratios may be applied without limitation to the methods described and described herein.

In a non-limiting example, the oligomerization conditions when forming the oligomeric product in the oligomerization process (s) or polyalphaolefin production process (s) are from 50 ° C to 165 ° C; Alternatively 55 [deg.] C to 160 [deg.] C; Alternatively 60 ° C to 155 ° C; Alternatively 65 캜 to 150 캜; Alternatively from 70 [deg.] C to 145 [deg.] C; Alternatively, an oligomerization temperature of from 75 캜 to 140 캜. In a non-limiting embodiment, the oligomerization conditions when forming the oligomeric product in the oligomerization process (s) or polyalphaolefin production process (s) are from 70 ° C to 90 ° C; Alternatively 90 ° C to 120 ° C; Or alternatively, an oligomerization temperature in the range of 110 &lt; 0 &gt; C to 140 &lt; 0 &gt; C.

In a non-limiting example, the oligomerization conditions when forming the oligomeric product in the oligomerization process (s) or polyalphaolefin production process (s) include oligomerization in an inert atmosphere. In some non-limiting embodiments, the inert atmosphere is substantially free of oxygen at the start of the reaction; Otherwise, there is practically no water; Or otherwise an atmosphere substantially free of oxygen and substantially free of water at the beginning of the reaction. In an embodiment, the water content is less than 100 ppm; Otherwise, less than 75 ppm; Otherwise, less than 50 ppm; Otherwise, less than 30 ppm; Otherwise, less than 25 ppm; Otherwise, less than 20 ppm; Otherwise, less than 15 ppm; Otherwise, less than 10 ppm; Otherwise, less than 5 ppm; Otherwise, less than 3 ppm; Otherwise, less than 2 ppm; Otherwise, less than 1 ppm; Alternatively, less than 0.5 ppm. In an embodiment, the O ₂ content is less than 100 ppm; Otherwise, less than 75 ppm; Otherwise, less than 50 ppm; Otherwise, less than 30 ppm; Otherwise, less than 25 ppm; Otherwise, less than 20 ppm; Otherwise, less than 15 ppm; Otherwise, less than 10 ppm; Otherwise, less than 5 ppm; Otherwise, less than 3 ppm; Otherwise, less than 2 ppm; Otherwise, less than 1 ppm; Alternatively, less than 0.5 ppm. In some embodiments, the inert atmosphere is anhydrous nitrogen; Alternatively, it may be anhydrous argon.

In a non-limiting embodiment, the oligomerization conditions when forming the oligomeric product in the oligomerization process (s) or the polyalphaolefin production process (s) include oligomerization in a substantially ethylene-deficient state. In some non-limiting embodiments, the oligomerization conditions for oligomer product formation are less than 10 psig ethylene partial pressure; Otherwise, less than 7 psig; Otherwise, less than 5 psig; Otherwise, less than 4 psig; Otherwise, less than 3 psig; Otherwise, less than 2 psig; Alternatively, performing oligomerization at less than 1 psig.

In a non-limiting embodiment, the oligomerization conditions when forming the oligomeric product in the oligomerization process (s) or the polyalphaolefin production process (s) include performing oligomerization substantially in the absence of hydrogen. In some non-limiting embodiments, the oligomerization conditions for oligomer product formation are less than 10 psig hydrogen partial pressure; Otherwise, less than 7 psig; Otherwise, less than 5 psig; Otherwise, less than 4 psig; Otherwise, less than 3 psig; Otherwise, less than 2 psig; Alternatively, performing oligomerization at less than 1 psig.

In a non-limiting embodiment, oligomerization conditions include oligomerization at hydrogen partial pressure when oligomerization products are formed in the oligomerization process (s) or polyalphaolefin production process (s). The partial hydrogen pressure in the oligomerization reaction may be any pressure of hydrogen that does not interfere with the oligomerization reaction. While not intending to be bound by theory, hydrogen can be used to control oligomer molecular weight in an oligomerization process. In some non-limiting embodiments, oligomeric hydrogen partial pressures for oligomer product formation of greater than or equal to 5 psig; Otherwise, 10 psig or more; Otherwise, greater than 50 psig; Otherwise, greater than 100 psig; Otherwise, over 200 psig; Otherwise, over 300 psig; Otherwise, greater than 400 psig; Otherwise, over 500 psig; Otherwise, at least 750 psig; Otherwise, 1000 psig or higher; Otherwise, 1250 psig or higher; Alternatively, performing oligomerization at 1500 psig or higher. In other non-limiting embodiments, the oligomerization conditions when forming the oligomeric product in the oligomerization process (s) or the polyalphaolefin production process (s) include 0 psig to 2000 psig hydrogen partial pressure; Alternatively from 1 psig to 1500 psig; Alternatively from 5 psig to 1250 psig; Alternatively 10 psig to 1000 psig; Alternatively 50 psig to 750 psig; Alternatively from 100 psig to 500 psig; Alternatively 150 psig to 400 psig; Alternatively, performing oligomerization in the range of 200 psig to 300 psig.

According to another aspect of the present invention, there are various properties of oligomeric products that can be achieved by applying the oligomerization methods described herein. In a non-limiting embodiment, at least 80% by weight of the alpha olefin monomer in the oligomerization process (s) or polyalphaolefin production process (s) is converted to the oligomer product; Alternatively, at least 85% by weight of the alpha olefin monomer is converted to the oligomer product; Alternatively, at least 90% by weight of the alpha olefin monomer is converted to the oligomer product. In an embodiment, the oligomer product comprises dimer, trimer, and heavy oligomer. In a non-limiting example, the oligomeric product in the oligomerization process (s) or polyalphaolefin production process (s) comprises at least 70% by weight of heavy oligomer; Alternatively at least 75% by weight of heavy oligomers; Alternatively, at least 77.5 wt% heavy oligomers; Alternatively at least 80% by weight of heavy oligomers; Alternatively at least 82.5 wt% of heavy oligomers; Alternatively at least 84% by weight of heavy oligomers; Or alternatively at least 85% by weight of the heavy oligomer.

According to any of the embodiments described herein, an oligomerization process forms an oligomerization reactor effluent comprising an oligomeric product, and the method further comprises the step of separating the oligomerization reactor effluent to form a heavy oligomer product. In this embodiment, at least a portion of the alpha olefin monomer, dimer, or trimer is removed from the oligomerization reactor effluent to form a heavy oligomer product. In a non-limiting embodiment, the heavy oligomer product in the oligomerization process (s) or polyalphaolefin production process (s) comprises less than 0.6% alpha olefin monomer; Alternatively less than 0.5% by weight alpha olefin monomer; Alternatively, less than 0.4% by weight alpha olefin monomer; Alternatively less than 0.3% by weight alpha olefin monomers; Alternatively, less than 0.2% by weight alpha olefin monomer; Or alternatively less than 0.1% by weight of alpha olefin monomers. In a non-limiting embodiment, the heavy oligomer product in the oligomerization process (s) or polyalphaolefin production process (s) comprises less than 2% dimer; Alternatively, less than 1.75 wt% dimer; Alternatively, less than 1.5 wt% dimer; Alternatively, less than 1.25 wt% dimer; Alternatively, less than 1% by weight dimer; Alternatively, less than 0.9 wt% dimer; Alternatively, less than 0.8 wt% dimer; Alternatively, less than 0.7 wt% dimer; Alternatively, less than 0.6 wt% dimer; Alternatively, less than 0.5 wt% dimer; Alternatively, less than 0.4 wt% dimer; Alternatively, less than 0.3 wt% dimer. In a non-limiting embodiment, the heavy oligomer product in the oligomerization process (s) or polyalphaolefin production process (s) comprises less than 10 wt% trimer; Alternatively, less than 7.5 wt% trimer; Alternatively, less than 5 wt% trimer; Alternatively, less than 3% by weight trimer; Alternatively, less than 2% by weight trimer; Alternatively, less than 1.75 wt% trimer; Alternatively, less than 1.5% by weight trimer; Alternatively, less than 1.25 wt% trimer; Alternatively, less than 1% by weight of trimer; Alternatively, less than 0.9 wt% trimer; Alternatively, less than 0.8 wt% trimer; Alternatively, less than 0.7 wt% trimer; Alternatively, less than 0.6% by weight trimer; Alternatively, less than 0.5% by weight trimer; Alternatively, less than 0.4% by weight trimer; Or alternatively less than 0.3% by weight of trimers. In a non-limiting embodiment, the heavy oligomer product in the oligomerization process (s) or polyalphaolefin production process (s) comprises at least 85% by weight of heavy oligomer; Alternatively at least 86% by weight of heavy oligomers; Alternatively at least 87% by weight of heavy oligomers; Alternatively at least 88% by weight of heavy oligomers; Alternatively at least 89 wt% of heavy oligomers; Alternatively at least 90% by weight of heavy oligomers; Alternatively at least 91% by weight of heavy oligomers; Alternatively at least 92% by weight of heavy oligomers; Alternatively at least 93% by weight of heavy oligomers; Alternatively at least 94% by weight of heavy oligomers; Or alternatively at least 94% by weight of the heavy oligomer. Other monomer content, dimer content, and heavy oligomer content can be applied without limitation to the methods described and described herein.

In one embodiment, a separation method of removing at least some of the monomer, dimer, and / or trimer from the oligomerization reactor effluent to form a heavy oligomer product comprises contacting at least a portion of the monomer, dimer, and / Any separation method that can be separated from the effluent can be used. In a non-limiting example, the separation may be distillation. In some embodiments, it may be a separate thin film distillation. In some non-limiting embodiments, the distillation or thin film distillation has less than 760 torr; Otherwise, less than 600 torr; Otherwise, less than 400 torr; Otherwise, less than 200 torr; Otherwise, less than 100 torr; Otherwise, less than 75 torr; Otherwise, less than 50 torr; Otherwise, less than 40 torr; Otherwise, less than 30 torr; Otherwise, less than 20 torr; Otherwise, less than 10 torr; Otherwise, less than 5 torr; Alternatively, at pressures less than one torr. In a non-limiting example, distillation or thin film distillation can be carried out by spraying an inert gas through a distillation apparatus or a thin film distillation apparatus. In an aspect, the jetting gas may be an inert gas. The propellant gas may be nitrogen, helium, argon, or a combination thereof; Otherwise, nitrogen; Alternatively, it may be helium, or otherwise argon.

According to certain embodiments as described herein, the polyalphaolefin production process (s) can produce polyalphaolefins having a preferred amount of hydrogenated alpha olefin monomer, hydrogenated dimer, hydrogenated trimer, and / or hydrogenated heavy oligomer have. In a non-limiting example, the heavy oligomer product in the oligomerization process (s) or polyalphaolefin production process (s) comprises less than 0.6% hydrogenated alpha olefin monomer; Alternatively, less than 0.5% by weight hydrogenated alpha olefin monomer; Alternatively, less than 0.4% by weight hydrogenated alpha olefin monomer; Alternatively less than 0.3% by weight hydrogenated alpha olefin monomers; Alternatively less than 0.2% by weight hydrogenated alpha olefin monomer; Or alternatively less than 0.1% by weight hydrogenated alpha olefin monomers. In a non-limiting embodiment, the heavy oligomer product in the oligomerization process (s) or polyalphaolefin production process (s) comprises less than 2 wt% hydrogenated dimer; Alternatively, less than 1.75 wt% hydrogenated dimer; Alternatively, less than 1.5 wt% hydrogenated dimer; Alternatively, less than 1.25 wt% hydrogenated dimer; Alternatively less than 1% by weight hydrogenated dimer; Alternatively, less than 0.9 wt% hydrogenated dimer; Alternatively, less than 0.8 wt% hydrogenated dimer; Alternatively, less than 0.7 wt% hydrogenated dimer; Alternatively, less than 0.6 wt% hydrogenated dimer; Alternatively less than 0.5% by weight hydrogenated dimer; Alternatively, less than 0.4 wt% hydrogenated dimer; Alternatively, less than 0.3 wt% hydrogenated dimer. In a non-limiting embodiment, the heavy oligomer product in the oligomerization process (s) or polyalphaolefin production process (s) comprises less than 10 wt% hydrogenated trimer; Alternatively less than 7.5% by weight of hydrogenated trimer; Alternatively less than 5% by weight of hydrogenated trimer; Alternatively less than 3% by weight of hydrogenated trimer; Less than 2 wt% hydrogenated trimer; Alternatively, less than 1.75 wt% hydrogenated trimer; Alternatively less than 1.5% by weight of hydrogenated trimer; Alternatively, less than 1.25 wt% hydrogenated trimer; Alternatively less than 1% by weight of hydrogenated trimer; Alternatively, less than 0.9 wt% hydrogenated trimer; Alternatively, less than 0.8 wt% hydrogenated trimer; Alternatively less than 0.7% by weight of hydrogenated trimer; Alternatively less than 0.6% by weight hydrogenated trimer; Alternatively less than 0.5% by weight hydrogenated trimer; Alternatively less than 0.4% by weight of hydrogenated trimer; Alternatively, less than 0.3% by weight hydrogenated trimer. In a non-limiting embodiment, the heavy oligomer product in the oligomerization process (s) or polyalphaolefin production process (s) comprises at least 85 wt% hydrogenated heavy oligomer; Alternatively at least 86 wt% hydrogenated heavy oligomer; Alternatively at least 87 wt% hydrogenated heavy oligomer; Alternatively at least 88 wt% hydrogenated heavy oligomer; Alternatively at least 89 wt% hydrogenated heavy oligomer; Alternatively at least 90% by weight hydrogenated heavy oligomer; Alternatively at least 91% by weight hydrogenated heavy oligomer; Alternatively at least 92 wt% hydrogenated heavy oligomer; Alternatively at least 93 wt% hydrogenated heavy oligomer; Alternatively at least 94 wt% hydrogenated heavy oligomer; Or alternatively at least 94% by weight hydrogenated heavy oligomer. Other hydrogenated monomer content, hydrogenated dimer content, and hydrogenated heavy oligomer content can be applied without limitation to the methods described and described herein.

In one embodiment, the oligomer product, the heavy oligomer product, and the polyalphaolefin may have desirable properties. In an embodiment, preferred properties are a predetermined 100 占 폚 kinematic viscosity, a predetermined viscosity index, a predetermined pour point, a predetermined flash point, a predetermined ignition point, a predetermined non-volatility, or any combination thereof; Alternatively, a predetermined 100 占 폚 kinematic viscosity, a predetermined viscosity index, a predetermined flash point, a predetermined flash point, or any combination thereof; Alternatively, a predetermined 100 占 폚 kinematic viscosity, a predetermined viscosity index, a predetermined pour point, or any combination thereof; Alternatively, a predetermined flash point, a predetermined flash point, or any combination thereof; Otherwise, a predetermined 100 ° C kinematic viscosity; Otherwise, a predetermined flash point; Otherwise, a predetermined ignition point; Or alternatively, some of the furnace volatility. Other combinations of properties of the heavy oligomer product and / or polyalphaolefin are apparent in the present invention.

In a non-limiting embodiment, the heavy oligomer product in the oligomerization process (s) or polyalphaolefin production process (s) has a kinematic viscosity at 100 ° C of from 25 cSt to 225 cSt; Otherwise, 25 cSt to 55 cSt; Alternatively 30 cSt to 50 cSt; Alternatively 32 cSt to 48 cSt; Otherwise, 35 cSt to 45 cSt; Alternatively 40 cSt to 80 cSt; Otherwise, 45 cSt to 75 cSt; Alternatively 50 cSt to 70 cSt; Alternatively 60 cSt to 100 cSt; Alternatively 65 cSt to 95 cSt; Alternatively 70 cSt to 90 cSt; Alternatively 80 cSt to 140 cSt; Alternatively 80 cSt to 120 cSt; Alternatively from 85 cSt to 115 cSt; Alternatively 90 cSt to 110 cSt; Alternatively 100 cSt to 140 cSt; Otherwise, from 105 cSt to 135 cSt; Alternatively 110 cSt to 130 cSt; Alternatively 110 cSt to 190 cSt; Otherwise, from 135 cSt to 175 cSt; Alternatively from 140 cSt to 160. In another non-limiting embodiment, the heavy oligomer product in the oligomerization process (s) or polyalphaolefin production process (s) has a 100 ° C kinematic viscosity of from 200 cSt to 300 cSt; Alternatively 220 cSt to 280 cSt; Otherwise, 235 to 265; Alternatively from 250 cSt to 350 cSt; Otherwise, 270 cSt to 330 cSt; Otherwise, 285 cSt to 315 cSt; Alternatively from 300 cSt to 400 cSt; Otherwise, 320 cSt to 380 cSt; Otherwise, 335 to 365; Alternatively from 350 cSt to 450 cSt; Otherwise, 370 cSt to 430 cSt; Otherwise, 385 cSt to 415 cSt; Alternatively 400 cSt to 500 cSt; Otherwise, 420 cSt to 480 cSt; Otherwise, 435 to 465; Otherwise, from 450 cSt to 550 cSt; Otherwise, 470 cSt to 530 cSt; Otherwise, 485 cSt to 515 cSt; Otherwise, 500 cSt to 700 cSt; Otherwise, 540 cSt to 660 cSt; Otherwise, 570 to 630; Otherwise, 600 cSt to 800 cSt; Alternatively 640 cSt to 760 cSt; Otherwise, 670 cSt to 740 cSt; Otherwise, 700 cSt to 900 cSt; Otherwise, 740 cSt to 860 cSt; Otherwise, 770 to 830; Otherwise, 800 cSt to 1,000 cSt; Otherwise, 840 cSt to 960 cSt; Otherwise, 870 cSt to 940 cSt; Otherwise, 900 cSt to 1,100 cSt; Otherwise, 940 cSt to 1,060 cSt; Alternatively, 970 to 1,030. Thus, broad kinetic constants are achieved by the method and catalyst of the present invention by altering the oligomerization conditions, as can be understood by those skilled in the art. Other &lt; RTI ID = 0.0 &gt; 100 C &lt; / RTI &gt; kinematic viscosity of the heavy oligomer is described herein and may be applied without limitation to the methods described.

In a non-limiting embodiment where the heavy oligomer product is hydrogenated, the polyalphaolefins in the oligomerization process (s) or polyalphaolefin production process (s) have a kinematic viscosity at 100 ° C of from 25 cSt to 225 cSt; Otherwise, 25 cSt to 55 cSt; Alternatively 30 cSt to 50 cSt; Alternatively 32 cSt to 48 cSt; Otherwise, 35 cSt to 45 cSt; Alternatively 40 cSt to 80 cSt; Otherwise, 45 cSt to 75 cSt; Alternatively 50 cSt to 70 cSt; Alternatively 60 cSt to 100 cSt; Alternatively 65 cSt to 95 cSt; Alternatively 70 cSt to 90 cSt; Alternatively 80 cSt to 140 cSt; Alternatively 80 cSt to 120 cSt; Alternatively from 85 cSt to 115 cSt; Alternatively 90 cSt to 110 cSt; Alternatively 100 cSt to 140 cSt; Otherwise, from 105 cSt to 135 cSt; Alternatively 110 cSt to 130 cSt; Alternatively 110 cSt to 190 cSt; Otherwise, from 135 cSt to 175 cSt; Alternatively from 140 cSt to 160. In another non-limiting embodiment where the heavy oligomer product is hydrogenated, the polyalphaolefins in the oligomerization process (s) or polyalphaolefin production process (s) have a kinematic viscosity at 100 DEG C of from 200 cSt to 300 cSt; Alternatively 220 cSt to 280 cSt; Otherwise, 235 to 265; Alternatively from 250 cSt to 350 cSt; Otherwise, 270 cSt to 330 cSt; Otherwise, 285 cSt to 315 cSt; Alternatively from 300 cSt to 400 cSt; Otherwise, 320 cSt to 380 cSt; Otherwise, 335 to 365; Alternatively from 350 cSt to 450 cSt; Otherwise, 370 cSt to 430 cSt; Otherwise, 385 cSt to 415 cSt; Alternatively 400 cSt to 500 cSt; Otherwise, 420 cSt to 480 cSt; Otherwise, 435 to 465; Otherwise, from 450 cSt to 550 cSt; Otherwise, 470 cSt to 530 cSt; Otherwise, 485 cSt to 515 cSt; Otherwise, 500 cSt to 700 cSt; Otherwise, 540 cSt to 660 cSt; Otherwise, 570 to 630; Otherwise, 600 cSt to 800 cSt; Alternatively 640 cSt to 760 cSt; Otherwise, 670 cSt to 740 cSt; Otherwise, 700 cSt to 900 cSt; Otherwise, 740 cSt to 860 cSt; Otherwise, 770 to 830; Otherwise, 800 cSt to 1,000 cSt; Otherwise, 840 cSt to 960 cSt; Otherwise, 870 cSt to 940 cSt; Otherwise, 900 cSt to 1,100 cSt; Otherwise, 940 cSt to 1,060 cSt; Alternatively, 970 to 1,030. Thus, broad kinetic constants are achieved by the method and catalyst of the present invention by altering the oligomerization conditions, as can be understood by those skilled in the art. Other 100 ° C kinematic viscosity of the polyalphaolefins is described herein and may be applied without limitation to the process described.

In a non-limiting embodiment, the heavy oligomer product and / or polyalphaolefin in the oligomerization process (s) or polyalphaolefin production process (s) has a viscosity index of from 150 to 260; Otherwise, 155 to 245; Otherwise, 160 to 230; Otherwise, 165 to 220; Otherwise, 170 to 220; Alternatively from 175 to 220. Other viscosity indexes of heavy oligomers and polyalphaolefins are described herein and may be applied without limitation to the methods described.

In a non-limiting embodiment, the heavy oligomer product and / or polyalphaolefin in the oligomerization process (s) or polyalphaolefin production process (s) has a pour point of less than 0 占 폚; Otherwise, less than -10 캜; Otherwise, less than -20 ° C; Otherwise, less than -30 ° C; Otherwise, less than -35 캜; Otherwise, less than -40 ° C; Otherwise, less than -45 캜; Otherwise, less than -50 ° C; Alternatively, less than -55 占 폚. In another non-limiting embodiment, the heavy oligomer product and / or the polyalphaolefin in the oligomerization process (s) or polyalphaolefin production process (s) has a pour point of from 0 캜 to -100 캜; Otherwise, between -10 ° C and -95 ° C; Alternatively -20 캜 to -90 캜; Otherwise, -30 캜 to -90 캜; Otherwise, from -35 ° C to -90 ° C; Alternatively -40 ° C to -90 ° C; Otherwise, -45 캜 to -90 캜; Alternatively -50 ° C to -85 ° C; Alternatively, from -55 ° C to -80 ° C. Other pour points of heavy oligomers and polyalphaolefins are described herein and may be applied without limitation to the methods described.

In a non-limiting embodiment, the polyalphaolefins in the polyalphaolefin production process (s) have a Bernoulli Index B (= 4 [ mm ] [ rr ] / [ mr ] ² ) of less than 3; Otherwise, less than 2.5; Otherwise, less than 2; Otherwise, less than 1.75; Otherwise, less than 1.7; Otherwise, less than 1.65; Otherwise, less than 1.6; Otherwise, less than 1.55; Otherwise, less than 1.5; Otherwise, less than 1.45; Otherwise, less than 1.4; Otherwise, less than 1.35; Otherwise, less than 1.3; Otherwise, less than 1.25; Otherwise, less than 1.25; Alternatively, may be less than 1.15. In a non-limiting embodiment, the polyalphaolefins in the polyalphaolefin production process (s) have a Bernoulli Index B (= 4 [ mm ] [ rr ] / [ mr ] ² ) of 1.4 ± 0.25; Otherwise, 1.4 ± 0.2; Otherwise, 1.4 ± 0.15; Otherwise, 1.4 ± 0.10; Otherwise, 1.3 ± 0.3; Otherwise, 1.3 ± 0.25; Otherwise, 1.3 ± 0.2; Otherwise, 1.3 ± 0.15; Otherwise, 1.4 ± 0.1; Otherwise, 1.2 ± 0.35; Otherwise, 1.2 ± 0.3; Otherwise, 1.2 ± 0.25; Otherwise, 1.2 ± 0.2; Otherwise, 1.2 ± 0.15; Otherwise, 1.1 ± 0.4; Otherwise, 1.1 ± 0.3; Otherwise, 1.1 ± 0.2; Alternatively, in the range of 1.1 ± 0.15. Polyalphaolefins and other Bernoulli indexes are described herein and may be applied without limitation to the methods described.

In a non-limiting embodiment, the polyalphaolefin in the oligomerization process (s) or polyalphaolefin production process (s) is at least 2,100 minutes; Otherwise, at least 2,200 minutes; Otherwise, at least 2,300 minutes; Or otherwise have an RPVOT determined according to ASTM D2272 in the presence of 0.5 wt% Naugalube (R) APAN antioxidant for at least 2,400 minutes. In another non-limiting embodiment, the polyalphaolefins in the oligomerization process (s) or the polyalphaolefin production process (s) are at least 2,000 min; Otherwise, at least 2,250 minutes; Otherwise, at least 2,500 minutes; Otherwise, at least 2,750 minutes; Or alternatively an RPVOT determined according to ASTM D2272 in the presence of 0.5 wt% Naugalube (R) APAN antioxidant for at least 3,000 minutes. Other RPVOT values of polyalphaolefins are described herein and may be applied without limitation to the process described.

The oligomerization and / or hydrogenation applied in the oligomerization process (s) or polyalphaolefin production process (s) of the present invention is carried out without diluent; Alternatively, it may be carried out using a diluent, or a solvent. The solvents used for oligomerization and / or hydrogenation in the oligomerization process (s) or polyalphaolefin production process (s) include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated aliphatic hydrocarbons, halogenated aromatic hydrocarbons, ; Aliphatic hydrocarbons; Otherwise, aromatic hydrocarbons; Otherwise, halogenated aliphatic hydrocarbons; Or alternatively, halogenated aromatic hydrocarbons. Useful aliphatic hydrocarbons as solvents include C ₃ to C ₂₀ aliphatic hydrocarbons; Alternatively, C ₃ to C ₁₅ aliphatic hydrocarbons; Or alternatively, C ₄ to C ₁₀ aliphatic hydrocarbons. Unless otherwise specified, aliphatic hydrocarbons may be cyclic or acyclic and / or linear or branched. Non-limiting examples of suitable non-cyclic aliphatic hydrocarbon solvents for use singly or in any combination include propane, iso-butane, butane, pentane (n-pentane or a mixture of linear and branched C ₅ non-cyclic aliphatic hydrocarbons) (n-hexane or a mixture of linear and branched C ₆ non-cyclic aliphatic hydrocarbons), heptane (n-heptane or a mixture of linear and branched C ₇ non-cyclic aliphatic hydrocarbons), octane, and combinations thereof. Non-limiting examples of suitable cyclic aliphatic hydrocarbon solvents include cyclohexane, methylcyclohexane. Useful aromatic hydrocarbons as solvents include C ₆ to C ₂₀ aromatic hydrocarbons; Or alternatively, C ₆ to C ₁₀ aromatic hydrocarbons. Non-limiting examples of aromatic hydrocarbons suitable for use singly or in any combination include benzene, toluene, xylene (including ortho-xylene, meta-xylene, para-xylene, or mixtures thereof) Or a combination thereof. Useful halogenated aliphatic hydrocarbons as solvents include C ₁ to C ₁₅ halogenated aliphatic hydrocarbons; Alternatively, C ₁ to C ₁₀ halogenated aliphatic hydrocarbons; Or alternatively, C ₁ to C ₅ halogenated aliphatic hydrocarbons. Unless otherwise specified, halogenated aliphatic hydrocarbons may be cyclic or acyclic and / or linear or branched. Non-limiting examples of halogenated aliphatic hydrocarbons suitable for use singly or in any combination include methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, and combinations thereof. Halogenated aromatic hydrocarbons useful as solvents include C ₆ to C ₂₀ halogenated aromatic hydrocarbons; Or alternatively, C ₆ to C ₁₀ halogenated aromatic hydrocarbons. Non-limiting examples of halogenated aromatic hydrocarbons suitable for use singly or in any combination include chlorobenzene, dichlorobenzene, and combinations thereof.

Oligomerization  Selective Examples

According to one aspect of the present invention, there is provided an oligomerization method comprising:

a) A contacting step of an alpha olefin monomer and a catalyst system comprising:

One) expression

,

,

,

을 가지는 메탈로센 또는 이들의 임의 조합, 여기에서:

,

,

,

Or any combination thereof, wherein: &lt; RTI ID = 0.0 &gt;

i) each of R ²⁰ , R ²¹ , R ²³ , and R ²⁴ independently represents hydrogen, a C ₁ to C ₂₀ alkyl group, or a C ₁ to C ₂₀ alkenyl group, and

iii) each of X ¹² , X ¹³ , X ¹⁵ , and X ¹⁶ is independently F, Cl, Br, or I;

2) A first activator comprising a chemically-treated solid oxide comprising fluorinated alumina, chlorinated alumina, sulfated alumina, fluorinated silica-alumina, or any combination thereof; And

3) a second activator comprising an organoaluminum compound having formula Al (X ¹⁰ ) _n (X ¹¹ ) _{3 -n} ; Wherein X ¹⁰ is independently a C ₁ to C ₂₀ hydrocarbyl, X ¹¹ is independently a halide, a hydride, or a C ₁ to C ₂₀ hydrocarboxylide; And n is a number from 1 to 3; And

b) And oligomer product formation under oligomerization conditions.

In a non-limiting embodiment, the metallocene is:

,

,

,

,

,

,

Or any combination thereof, wherein: &lt; RTI ID = 0.0 &gt;

i) each of R ²⁰ , R ²¹ , and R ²³ is independently hydrogen, a C ₁ to C ₁₀ alkyl group, or a C ₁ to C ₁₀ alkenyl group, and

iii) each of X ¹² , X ¹³ , and X ¹⁵ is independently Cl or Br.

In another non-limiting embodiment, the metallocene is:

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

Or any combination of these structures.

Also in a non-limiting embodiment, the metallocene is:

,

,

, 또는 이들의 임의 조합을 포함하거나, 실질적으로 이루어지거나, 또는 이루어진다. 올리고머화 방법 및 올리고머화 방법에 의해 생성되는 물질의 추가적인 실시예 및 요소는 본 개시로부터 명백하다.

,

,

, &Lt; / RTI &gt; or any combination thereof. Additional embodiments and elements of materials produced by oligomerization methods and oligomerization methods are apparent from this disclosure.

According to a further aspect of the present invention there is provided an oligomerization process comprising the steps of contacting an alpha olefin monomer and a catalyst system and forming an oligomerization reactor effluent comprising an oligomer product under oligomerization conditions, Wherein at least some of the alpha olefin monomer, dimer, or trimer is removed from the oligomerization reactor effluent to form a heavy oligomer product wherein: the oligomerization reactor effluent separation step comprises:

1) the alpha olefin monomer is substantially composed of a C ₈ normal alpha olefin;

2) The catalyst system comprises

i) expression

을 가지는 메탈로센, 여기에서

A metallocene having

(1) each R ²⁰ is independently hydrogen, a C ₁ to C ₁₀ alkyl group, or a C ₁ to C ₁₀ alkenyl group, and

(2) each X ¹² is independently Cl or Br;

ii) A first activator comprising fluorinated silica-alumina; And

iii) A second activator comprising trialkyl aluminum; And

3) The oligomerization temperature is from 90 캜 to 120 캜;

4) The 100 캜 dynamic viscosity of the heavy oligomer product is 30 cSt to 50 cSt; And

5) Heavy oligomer products include the following.

i) Less than 0.5% by weight alpha olefin monomer;

ii) Less than 1% by weight dimer; And

iii) At least 88% by weight of heavy oligomers.

In some non-limiting embodiments, the metallocene is:

,

, 또는 이들의 임의 조합을 포함하거나, 실질적으로 이루어지거나, 이루어진다.

,

, &Lt; / RTI &gt; or any combination thereof.

In some embodiments, the viscosity index of the heavy oligomer product is from 150 to 260. In another non-limiting embodiment, the heavy oligomer product is hydrogenated to provide a polyalphaolefin. In other non-limiting examples in which the heavy oligomer product is hydrogenated to provide a polyalphaolefin, the polyalphaolefin has a pour point of -30 캜 to -90 캜. In further embodiments in which the heavy oligomer product is hydrogenated to provide a polyalphaolefin, the polyalphaolefin has an RPVOT measured according to ASTM D2272 in the presence of 0.5 wt% Naugalube (R) APAN antioxidant for at least 2,100 minutes. In further non-limiting embodiments wherein the heavy oligomer product is hydrogenated to provide a polyalphaolefin, the polyunsaturated olefin has a Bernoulli index of less than 1.65; Alternatively in the range of 1.4 +/- 0.25. In some embodiments, the polyalphaolefins do not have crystallisations that are discernible above -40 DEG C when measured by differential scanning calorimetry according to ASTM D 3418. Additional embodiments and elements of materials produced by oligomerization methods and oligomerization methods are apparent from this disclosure.

Another aspect of the present invention provides an oligomerization process comprising the steps of forming an oligomerization reactor effluent comprising an oligomeric product under the conditions of contacting the alpha olefin monomer and the catalyst system and under oligomerization conditions, Wherein at least some of the alpha olefin monomer, dimer, or trimer is removed from the oligomerization reactor effluent to form a product of a heavy oligomer, wherein:

1) the alpha olefin monomer is substantially composed of a C ₈ normal alpha olefin;

2) The catalyst system comprises

i) expression

을 가지는 메탈로센, 여기에서

A metallocene having

(1) each R ²⁰ is independently hydrogen, a C ₁ to C ₁₀ alkyl group, or a C ₁ to C ₁₀ alkenyl group, and

(2) each X ¹² is independently Cl or Br;

ii) A first activator comprising fluorinated silica-alumina; And

iii) A second activator comprising trialkyl aluminum;

3) The oligomerization temperature is from 70 캜 to 90 캜;

4) The 100 캜 dynamic viscosity of the heavy oligomer product is 80 cSt to 140 cSt; And

5) Heavy oligomer products include the following.

i) Less than 0.5% by weight alpha olefin monomer;

ii) Less than 1% by weight dimer; And

iii) At least 88% by weight of heavy oligomers.

In some non-limiting embodiments, the metallocene is:

,

, 또는 이들의 임의 조합을 포함하거나, 실질적으로 이루어지거나, 이루어진다.

,

, &Lt; / RTI &gt; or any combination thereof.

In some embodiments, the viscosity index of the heavy oligomer product is from 150 to 260. In another non-limiting embodiment, the heavy oligomer product is hydrogenated to provide a polyalphaolefin. In other non-limiting embodiments in which the heavy oligomer product is hydrogenated to provide a polyalphaolefin, the pour point of the polyalphaolefin is from -30 캜 to -90 캜. In another embodiment where the heavy oligomer product is hydrogenated to provide a polyalphaolefin, the polyalphaolefin has an RPVOT determined according to ASTM D2272 in the presence of 0.5 wt% Naugalube (R) APAN antioxidant for at least 2,100 minutes. In further non-limiting embodiments in which the heavy oligomer product is hydrogenated to provide a poly alpha olefin, the poly-alpha olefin has a Bernoulli index of less than 1.65; Alternatively, in the range of 1.1 + -0.4. In some embodiments, the polyalphaolefins do not have crystallisations that are discernible above -40 DEG C when measured by differential scanning calorimetry according to ASTM D 3418. Additional embodiments and elements of materials produced by oligomerization methods and oligomerization methods are apparent from this disclosure.

Another aspect of the present invention provides an oligomerization process comprising the steps of forming an oligomerization reactor effluent comprising an oligomeric product under the conditions of contacting the alpha olefin monomer and the catalyst system and under oligomerization conditions, Wherein at least some of the alpha olefin monomer, dimer, or trimer is removed from the oligomerization reactor effluent to form a product of a heavy oligomer, wherein:

1) the alpha olefin monomer is substantially composed of a C ₈ normal alpha olefin;

2) The catalyst system comprises

i) expression

을 가지는 메탈로센, 여기에서

A metallocene having

(1) each of R ²³ and R ²⁴ independently represents hydrogen, a C ₁ to C ₁₀ alkyl group, or a C ₁ to C ₁₀ alkenyl group, and

(2) each X ¹⁵ is independently Cl or Br;

ii) A first activator comprising fluorinated silica-alumina; And

iii) A second activator comprising trialkyl aluminum;

3) The oligomerization temperature is from 110 캜 to 140 캜;

4) The 100 캜 dynamic viscosity of the heavy oligomer product is 80 cSt to 140 cSt; And

5) Heavy oligomer products include the following.

i) Less than 0.4% by weight alpha olefin monomer;

ii) Less than 1.5% dimer; And

iii) At least 88% by weight of heavy oligomers.

In some non-limiting embodiments, the metallocene is:

을 포함하거나, 실질적으로 이루어지거나, 이루어진다.

Or may be made substantially.

In some embodiments, the viscosity index of the heavy oligomer product is from 150 to 260. In another non-limiting embodiment, the heavy oligomer product is hydrogenated to provide a polyalphaolefin. In other non-limiting embodiments in which the heavy oligomer product is hydrogenated to provide a polyalphaolefin, the pour point of the polyalphaolefin is from -30 캜 to -90 캜. In another embodiment where the heavy oligomer product is hydrogenated to provide a polyalphaolefin, the polyalphaolefin has an RPVOT determined according to ASTM D2272 in the presence of 0.5 wt% Naugalube (R) APAN antioxidant for at least 2,100 minutes. In further non-limiting embodiments in which the heavy oligomer product is hydrogenated to provide a poly alpha olefin, the poly-alpha olefin has a Bernoulli index of less than 1.65; Alternatively, in the range of 1.1 + -0.4. In some embodiments, the polyalphaolefins do not have crystallisations that are discernible above -40 DEG C when measured by differential scanning calorimetry according to ASTM D 3418. Additional embodiments and elements of materials produced by oligomerization methods and oligomerization methods are apparent from this disclosure.

In another embodiment, the process may comprise a blend step of a polyalphaolefin and at least a second polyalphaolefin. In this aspect of the oligomerization process,

a) The 100 占 폚 dynamic viscosity of the second polyalphaolefin is at least 10 cSt different from the polyalphaolefin;

b) The second polyalphaolefin is produced using a different monomer than the polyalphaolefin; or

c) The 100 占 폚 kinematic viscosity of the second polyalphaolefin is at least 10 cSt above the polyalphaolefin and the second polyalphaolefin is produced using a different monomer than the polyalphaolefin.

Reactor

For the purposes of this disclosure, the term oligomerization reactor includes any oligomerization or oligomerization reactor system known in the art that is capable of oligomerizing certain alpha olefin monomers to produce the olefin oligomer product according to the present invention. An oligomerization reactor suitable for the present invention comprises at least one feed system, at least one feed system for catalyst systems or catalyst system components, at least one reactor system, at least one oligomer recovery system, or any suitable combination thereof It is possible. Reactors suitable for the present invention may also include a catalyst storage system, a catalyst component storage system, a cooling system, a diluent or solvent regeneration system, a monomer regeneration system or a control system, or a combination thereof. Such reactors may include continuous withdrawal and direct regeneration of catalysts, diluents, and oligomers. In general, continuous processes include continuous introduction of alpha olefin monomers, catalysts, and diluents into an oligomerization reactor and continuous removal of the suspension comprising the polymeric alpha olefin oligomer, catalyst system and diluent or solvent (s) from the reactor You may.

The oligomerization reactor system of the present invention may comprise a multiple reactor system comprising one type of reactor per system or two or more types of reactors operated in series in parallel. Multiple reactor systems may include reactors or unconnected reactors coupled together to effect oligomerization. The alpha olefin monomers are oligomerized in one reactor under one set of conditions and then the reactor effluent comprising the alpha olefin oligomer (and the potential catalyst system of the first reactor and / or the unreacted alpha olefin monomer) Lt; RTI ID = 0.0 &gt; oligomerization &lt; / RTI &gt;

In one aspect of the invention, the oligomerization reactor system may include at least one loop slurry reactor. Such reactors are well known in the art and may include vertical or horizontal loops. Such loops may include a loop or a series of loops. The plurality of loop reactors may include both vertical and horizontal loops. The oligomerization can be carried out in the presence of an organic diluent or solvent which can utilize the alpha olefin monomer as a liquid carrier or disperse and / or transport the catalyst system component and / or the catalyst system. The organic solvent may be used to lower the viscosity of the reaction mixture (including alpha olefin oligomers) and to allow the reaction mixture to flow or be easily transported through the processing apparatus. The solvents described herein can be applied without limitation for dispersing and / or transporting the catalyst system. The monomer (s), solvent, catalyst system component, and / or catalyst system may be fed into a loop reactor where successive oligomerization takes place.

In another embodiment, the oligomerization reactor comprises a tubular reactor. The tubular reactor has several zones into which new monomer, catalyst system, and / or catalyst system components (and / or oligomerization reaction other components, such as hydrogen) are introduced. The monomers are introduced into the reactor zone and the catalyst system, and / or the catalyst components (and / or oligomerization reaction other components, such as hydrogen) are introduced into the other zones of the reactor. Heat and pressure create optimum oligomerization reaction conditions.

In another aspect of the invention, the oligomerization reactor comprises a solution oligomerization reactor. In the solution oligomerization process, the alpha olefin monomer is contacted with the catalyst system and / or catalyst system components by suitable stirring or other means. Carriers containing inert organic diluents (if used) or excess monomers may be applied. If necessary, in the presence or absence of a liquid material, the monomer is contacted with the catalytic reaction product in a gaseous phase. The oligomerization zone is maintained at a temperature and pressure sufficient to form an oligomer product solution in the reaction medium. Stirring proceeds in the oligomerization process to maintain a good temperature control and uniform oligomerization mixture throughout the oligomerization zone. Suitable means for dissipating oligomerization fever may be applied. The oligomerization may be carried out batchwise or continuously. The reactor may comprise a series of at least one separating device using high pressure and / or low pressure to separate the desired oligomer.

According to another aspect of the present invention, an oligomerization reactor system may comprise a combination of two or more reactors. The preparation of oligomers in multiple reactors may involve several steps in at least two separate oligomerization reactors interconnected by a transfer device, wherein the transfer device transfers the oligomer produced from the first oligomerization reactor to a second polymerizer . The preferred oligomerization conditions in one of the reactors may be different from the working conditions of the other reactors. Alternatively, oligomerization in multiple reactors may involve manual delivery of oligomers from one reactor to subsequent reactors for subsequent oligomerization. Such reactors may include, but are not limited to, any combination including a multiple loop reactor, a multiple solution reactor, a multiple stirred tank reactor or multiple autoclave reactors.

In one embodiment, the process includes a separation step or a multiple separation step to remove at least some unreacted monomer, dimer, and / or trimer. In one embodiment, the separation step (s) is operated to reduce the monomer, dimer, and / or trimer content in the reactor effluent and / or the olefin oligomer product. Preferred monomer, dimer, and / or trimer contents are applied without limitation to the description of the separation step (s) described herein. The separation step (s) may be applied to remove the diluent or solvent from the alpha olefin oligomer, if necessary.

In another embodiment, the process comprises a separation step or a multiple separation step to provide an alpha olefin oligomer product (or an oligomer product), or an alpha olefin oligomer product to provide a poly alpha olefin having desirable properties. One of the desirable properties that can be achieved by applying the separation step or steps is a 100 占 폚 kinematic viscosity. A preferred secondary property that can be achieved by applying the separation step or steps is to obtain the desired flash point. A preferred tertiary characteristic that can be achieved by applying separation steps or steps is to achieve the desired flash point. A preferred quaternary property which can be achieved by applying the separation step or steps is to achieve the desired kneading volatility. In an embodiment, the separation step (s) can be carried out in the presence of an alpha-olefinic oligomeric product capable of producing polyalphaolefins having a preferred 100 ° C kinematic viscosity, a flash point, a flash point, and / / &Lt; / RTI &gt; or high molecular weight oligomers. In another embodiment, the separation step (s) can be applied to produce a plurality of alpha olefin oligomer products, or a plurality of alpha olefin oligomer products, which are capable of producing polyalphaolefins having a preferred 100 DEG C kinematic viscosity. In another embodiment, the separation step (s) can be applied to produce a product having a preferred 100 ° C kinematic viscosity and a particular flash point. The preferred 100 占 폚 kinematic viscosity, flash point, and flash point for the alpha olefin oligomer product (s) are not limited to being described herein and further describing the olefin oligomer product, heavy oligomer product, and / or polyalphaolefin separation step (s) .

In some embodiments, additives and modifiers are added to the polyalphaolefins to provide the desired properties or effects. Applying the invention described herein can produce PAOs that can be used as lubricants or synthetic oils and the like at low cost while retaining most or all of the unique properties of oligomers produced with metallocene catalysts.

All publications and patents mentioned herein are incorporated by reference in their entirety for the purpose of describing and disclosing the design and methodology described in these publications that may be used in connection with the methods of the present invention. The publications and patents discussed above and throughout the text are provided solely for their disclosure prior to the filing date of the present application. Nothing herein should be construed as an admission that the inventors are not entitled to antedate such publication by virtue of prior invention.

Unless otherwise indicated, when any type of range is disclosed and claimed, such as numerical ranges such as carbon atoms, viscosity, viscosity index, pour point, Bernoulli index, temperature, and the like, - Intention to initiate or claim each individual possible value, including scope. For example, when a numerical range of carbon atoms is described, the range encompasses the range between each possible individual integer included in the range and the integer number of atoms. Thus, it is contemplated by the Applicant's intent that if the alkyl groups are disclosed as C ₁ to C ₁₀ alkyl groups or alkyl groups having "up to" 1 to 10 carbon atoms or up to 10 carbon atoms, the alkyl groups will have 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms, and these methods of describing such groups may be used interchangeably. When describing a measurement range, such as a viscosity index, all possible values that this range may reasonably refer to are, for example, one or more ranges of values greater than the range end numerical value. The viscosity indices between 190 and 200 in this example individually include viscosity indices 190, 191, 192, 193, 194, 195, 196, 197, 198, 199, Applicant's intent is that the two methods describing this range are used interchangeably. Also, when a numerical range is disclosed or claimed, the applicant &apos; s intent reflects the respective respective possible values that this range reasonably covers, and also that the applicant reflects the disclosure of the ranges, their interchangeable, And any sub-ranges and combinations thereof. In this embodiment, the applicant intention to disclose C ₁ to C ₁₀ is that the alkyl group is optionally substituted with _one or more substituents selected from the group consisting of C ₁ to C ₆ alkyl, C ₄ to C ₈ alkyl, C ₂ to C ₇ alkyl, C ₁ to C _3, and C ₅ to C ₇ alkyl And the like, and the like. Applicant therefore has the right to preclude or exclude any individual member of any such group, any sub-range or sub-range combination within the group, and for any reason whatsoever, for example, The applicant may claim less than the complete indication as set forth in the preceding paragraph.

In an arbitrary application filed with the United States Patent and Trademark Office, this abstract contains 37 C.F.R. §1.72, and 'to allow the United States Patent and Trademark Office and the public to review this technical disclosure feature and subject matter generally through a superficial review'. §1.72 (b) for the purpose. Accordingly, the present summary should not be used to interpret the claims or limit the scope of the subject matter disclosed herein. In addition, any subject matter applied to it should not be used as an interpretation of the claims or as an intention to limit the scope of the subject matter disclosed herein. Using a past tense that describes an embodiment that would otherwise have been described constructively and predictably does not reflect the fact that the constructive and predictive embodiment is actually being performed.

For any particular compound described herein, the general structural formulas include all stereoisomers and stereoisomers that are produced by a particular set of substituents unless otherwise indicated. Thus, the general formulas include all enantiomers, diastereomers, and optical isomers, as the context permits and when necessary, irrespective of the enantiomeric or racemic form or mixture of stereoisomers. In any given formula given, any of the generic formulas presented includes all the stereoisomers, positional isomers, and stereoisomers that are produced due to a particular set of substituents.

The present invention is further illustrated by the following examples, which are not to be construed as limiting the scope of the invention. On the contrary, it is to be understood that various other aspects, embodiments, modifications, and equivalents thereof may be suggested to one skilled in the art after reading the specification herein without departing from the spirit of the invention or the scope of the appended claims. Clearly understood.

In the following examples, unless otherwise specified, the synthesis and preparation described were carried out in an inert atmosphere such as nitrogen and / or argon. Solvents were purchased from commercial manufacturers and were typically dried prior to use. Unless otherwise specified, reagents were obtained from commercial manufacturers.

General experimental procedure

Alpha olefin Oligomerization  General procedure

Unless otherwise specified, the general procedure applied to alpha olefin oligomerization is as follows. The alpha olefins discharged or injected using a nitrogen stream for several hours were dried on a 13x molecular sieve in an inert atmosphere. Using a heating mantle, the flask with the olefin sample was heated to the desired reaction temperature and stirred to maintain a uniform temperature and mixing. The flask was connected to an oil bubbler for a typical safety experiment. When using the alkyl aluminum component, the alkyl aluminum component was first added to the flask, followed by the addition of a hydrocarbon solution of toluene, olefin, or other metallocene (typically 0.5-10 mg / ml). Subsequently, a chemically treated solid oxide (solid superacid) activator was added. The order of addition of these reagents may vary, but typically the alkylaluminum component may be added first to remove residual moisture in the olefin. The addition of a solid acid catalyst does not typically produce appreciable exotherms, but if a fuming reaction is observed, the catalyst and activator content is reduced to reduce the initial exotherm to less than 5 ° C. This slight initial exotherm typically emanates after a few minutes and the reaction temperature falls to the desired set point, where it is maintained for the duration of the reaction. All procedures were carried out under inert atmosphere conditions.

For alpha olefin oligomerization reactions performed in a hydrogen atmosphere, this general procedure was carried out in Autoclave Engineers' Zipperclave ™ reactor at the preferred hydrogen pressure. The reaction temperature was lowered and several milliliters of water were added to remove the residual catalyst to separate the product. If necessary and / or to facilitate filtration, a volatile solvent such as n-pentane is added and the precipitated catalyst components and solid acid are removed by filtration. The lower molecular weight components were removed by vacuum distillation to yield the distilled oligomer product.

Brookfield  Viscosity

The -8 ° C, -20 ° C, -26 ° C, and -40 ° C Brookfield viscosities for alpha olefin oligomers, hydrogenated oligomers, or commercially available PAO were determined according to ASTM D5133 at the temperatures mentioned, It is reported as Poise (cP).

Gel permeation chromatography ( GPC ) Molecular weight and molecular weight distribution by method

The molecular weight average was obtained by applying a single-column method to a Polymer Labs PL-gel MIXED-E column. The column packed particle size was 3 microns and the column dimensions were 300 mm x 7.5 mm. A differential refractometer was used. A four-component polystyrene calibration standard with molecular weights of 1000, 4000, 20,000, and 50,000 was used and the coefficient of determination of secondary fidelity to calibration points was 0.998. These calibration curves were used to generate molecular weight data for the reported examples.

DSC  Method

Differential Scanning Calorimetry (DSC) analysis was performed with a Perkin-Elmer DSC-7 at a nitrogen flow rate of 20 cc / min (cubic centimeters per minute). The temperature program was applied as follows:

Maintained at -60 &lt; 0 &gt; C for 5 minutes;

Heating from -60 DEG C to 100 DEG C at 10 DEG C / min;

Cooling from 100 占 폚 to -60 占 폚 at 10 占 폚 / min;

Maintained at -60 &lt; 0 &gt; C for 5 minutes; And

Heat from -60 ° C to 100 ° C at 10 ° C / min.

Shear stability

Shear Stability Standard The test method was determined according to ASTM D6278-07. The ASTM method is to evaluate the percentage loss in viscosity of the oligomer-containing fluid as a result of oligomer degradation in a high shear nozzle device with minimal thermal or oxidative effects.

KRL  Shear stability

The KRL shear stability (20 hours) of the alpha olefin oligomer, hydrogenated oligomer, or commercially available PAO was determined in accordance with DIN 51350 and the results are reported in terms of percentage loss in viscosity or percentage.

Kinematic viscosity

The 100 占 폚 kinematic viscosity and the 40 占 폚 kinematic viscosity of the alpha olefin oligomer are determined according to ASTM D445 or D742 at 100 占 폚 and 40 占 폚, and the results are reported in centistokes (cSt).

Viscosity index

The viscosity index is determined according to ASTM D2270 using the table provided for viscosity data determined at 100 캜 and 40 캜.

Pour point

The pour point is the temperature at which the sample flows under carefully controlled conditions. The pour point is determined according to ASTM D 5950 or D97 as described and the results are reported in degrees Celsius. When the lubricating base oil has a low pour point, it has other good low temperature properties such as low rolling point, low low temperature filter clogging point, and low temperature crank viscosity.

flash point

The flash point is determined by the Cleveland Open System (COC) method according to ASTM D92 and the results are reported in ° C.

flash point

The ignition point is determined by the Cleveland Open System (COC) method according to ASTM D92, and the results are reported in ° C.

Anodic  Volatile experiment

Noak volatility is measured according to ASTM D5800 and is reported in weight percent, which determines the evaporation loss of hydrogenated oligomers or commercially available PAOs under high temperature service conditions.

RPVOT  Oxidation stability experiment

RPVOT oxidation stability is determined according to ASTM D2272. This procedure measures the time at which a 25.4 psi pressure drop is obtained when oxygen is reacted with a hydrogenated oligomer or PAO sample under specified conditions and the longer the time, the higher the oxidation stability is reflected. According to the ASTM D2272 specification, the samples are oxidized under initial pressure in a stainless steel pressure vessel at about 150 ° C in which Chemtura's 0.5% Naugalube® APAN (alkylated phenyl-α-naphthylamine) antioxidant, copper catalyst, and water are present.

Catalyst system component

Various metallocene compound manufacturing processes that can be used in the metallocene manufacture disclosed herein have been reported. For example, U.S. Patent Nos. 4,939,217, 5,191,132, 5,210,352, 5,347,026, 5,399,636, 5,401,817, 5.42032 million, 5,436,305, 5,451,649, 5,496,781, 5,498,581, 5,541,272, 5,554,795, 5,563,284, 5,565,592, 5.57188 million, 5,594,078, 5,631,203, 5,631,335, 5,654,454, 5.66823 million, 5,705,579 , And 6,509, 427 describe such methods, each of which is incorporated herein by reference in its entirety. Other Processes for the Preparation of Metallocene Compounds: Koeppl, A. Alt, H. G. J. Mol. Catal A. 2001, 165, 23; Kajigaeshi, S .; Kadowaki, T .; Nishida, A .; Fujisaki, S. The Chemical Society of Japan, 1986, 59, 97; Alt, H. G .; Jung, M .; Kehr, G. J. Organomet. Chem. 1998, 562, 153-181; and Alt, H. G .; Jung, M. J. Organomet. Chem. 1998, 568, 87-112; Each of which is incorporated herein by reference in its entirety. In addition, other processes for preparing metallocene compounds are reported in Journal of Organometallic Chemistry, 1996, 522, 39-54, which is incorporated herein by reference in its entirety. The following articles also describe this method: Wailes, P. C .; Coutts, R. S. P .; Weigold, H. in Organometallic Chemistry of Titanium, Zironium, and Hafnium, Academic; New York, 1974.; Cardin, D. J .; Lappert, M. F .; and Raston, C. L .; Chemistry of Organo-Zirconium and -Hafnium Compounds; Halstead Press; New York, 1986; Each of which is incorporated herein by reference in its entirety.

Catalyst Metallocene  compound

The metallocenes applied in the examples are provided in Table 1 with reference designators. These reference signs are used throughout to refer to the metallocenes applied to the embodiments.

The metallocenes &lt; RTI ID = 0.0 &gt; Metallocene
Indicator rescue Metallocene
Indicator rescue A

B

C

D

E

F

G

H

I

J

K

L

M

N

O

P

Q

R

S

T

U

V

W

X

Y

The methylated alumoxane (MMAO) used in the examples is an isobutyl-modified methylalumoxane and is available from Akzo Nobel having an approximate formula [(CH ₃ ) _0.7 ( iso- C ₄ H ₉ ) _0.3 AlO] _n It is a commercial product and is used as a toluene solution.

Example 1

Fluorinated silica-alumina activator-support preparation

The silica-alumina used in the preparation of the fluorinated silica-alumina acidic activator-support in this example contains 13% alumina in WR Grace, a pore volume of about 1.2 cc / g and a surface area of about 400 m ² / g MS 13 -110. &Lt; / RTI &gt; The material was fluorinated by initial wet impregnation with a sufficient amount of an ammonium-containing solution containing an amount of ammonium corresponding to 10% by weight of the silica-alumina weight. The impregnated material was dried at 100 &lt; 0 &gt; C for 8 hours under vacuum. The fluorinated silica-alumina samples thus produced were fired as follows. About 10 grams of fluorinated silica-alumina was placed in a 1.75-inch quartz tube with a sintered quartz disk on the bottom. The fluorinated silica-alumina was placed on the disc and the dry air was blown through the disc at a linear velocity of about 1.6 to 1.8 standard cubic feet per hour. The tube temperature around the quaternary tube was increased to a final temperature of about 450 ° C at a rate of about 400 ° C per hour. At this temperature, silica-alumina was flowed in dry air for 3 hours. Thereafter, the silica-alumina was used without being subjected to a striking, stored in anhydrous nitrogen and exposed to the atmosphere.

Example 2

Chlorinated alumina activator-support preparation

10 mL of Ketjen (TM) grade B alumina was calcined in air at 600 DEG C for 3 hours. After this calcination step, the furnace temperature was lowered to about 400 ° C, the nitrogen stream was started over the alumina phase, and 1.0 mL of carbon tetrachloride was then injected into the nitrogen stream to vaporize the alumina phase upstream. The gaseous CCl ₄ was transported onto the surface and reacted with alumina to chlorinate the surface. Approximately 15.5 mmol chlorine ion per gram of dehydrated alumina was provided in this method. After the chlorination treatment, the produced alumina was white.

Example 3

Fluorinated alumina activator-support preparation

The alumina can be fluorinated in the same manner as in Example 1 for silica-alumina. The fluorinated alumina was calcined according to the procedure of Example 1, stored in anhydrous nitrogen, and used without exposure to the atmosphere.

Example 4

Sulfation  Alumina activator-support preparation

Ketjen ™ L 652 g alumina were impregnated with 137 g (NH _{4) 2} SO ₄ containing solution by incipient wetness or more dissolved in 1300 mL water. The mixture was placed in a vacuum oven, dried overnight in a semi-vacuum atmosphere at 110 ° C and calcined in a muffle furnace at 300 ° C for 3 hours and then at 450 ° C for 3 hours, after which the activated support was passed through an 80 mesh screen. The support was activated in air at 550 DEG C for 6 hours, and the thus chemically-treated solid oxide was stored in nitrogen until used.

Example 5

Preparation of high-viscosity polyalphaolefins ( PAO ) using metallocene and MMAO activator combinations

High-viscosity alpha olefin homo oligomers and co-oligomers (PAO) can be prepared using the various metallocenes and iso- butylated methyl aluminoxane (MMAO) as catalyst system components, with reference to the oligomerization operation shown in Table 2 below &Lt; / RTI &gt;

 Autoclave Engineers' Zipperclave ™ reactor was used for any oligomerization reactions requiring hydrogen. The catalysts listed in Table 2 were dissolved in a small amount of toluene in an NMR tube, sealed and connected to a clean drying reactor stirring shaft. The reactor was evacuated and the olefin / MMAO solution was charged. The hydrogen was partly filled and the reactor stirrer was activated to break the NMR tube and activate the catalyst. The hydrogen pressure was then increased to the desired reactor pressure and fed "on demand" using a TESCOM regulator. The reaction mixture was diluted in pentane and the catalyst components were removed by filtration to separate out the product, followed by distillation and / or evaporation to remove volatiles and obtain PAO.

Table 2 shows the oligomerization conditions and alpha olefin oligomer properties provided by applying the metallocene and MMAO activator combinations.

Oligomerization and oligomerization of alpha olefin oligomers (PAO) prepared using metallocene and MMAO activator combinations Example No. Catalyst & Content
(mg) MMAO
Al: Zr ratio Feed ^A (grams) H ₂ (psig) Ti (占 폚)
T _max (° C) Conv. (%) Mn 100 C visc. (cSt) Pour Point (℃) 5A A (7.2) 1000 C ₈ (143), C ₁₄ (155) 600 41
- 55 - 644 -29 5B A (6.0) 1000 C ₈ (286) 600 25
51 - M _n = 7920 986 -27 5C A (3.0) 1000 C ₈ (143) 75 25
- 61 M _n = 7590 1372 -18 5D A (3.0) 1000 C ₈ (143) 0 25
25 69 M _n = 9330 1119 -27 5E B (5.7) 1000 C ₈ (286) 600 25
41 - M _n = 7090 831 -24 5F B (10.0) 1000 C ₈ (286) 0 25
50 91 M _n = 5290 582 -28 5G B (8.5) 1000 C ₁₀ (286) 0 25
40 - M _n = 9840 917 -28 5H B (18) 1000 C ₁₂ (286) 0 25
40 - M _n = 9480 437 -25 5I A (6.0) 1000 1- _C14 (310)
1-C ₄ (240) 600 25

103 - M _n = 3700
M _w = 12500 529 18 5J A (4.0) 1000 1-C ₁₄ (388)
1-C ₄ (120) 600 25

Unknown - M _n = 9980
M _w = 22000 - 3 5K C (6.3) 1000 1- _C14 (310)
1-C ₄ (240) 0 75

75 - M _n = 21200
M _w = 27300 - - 5L A (3.0) 1000 1- _C14 (155)
1-C ₄ (120) 300 25
- - 774 -31 5M A (6.0) 1000 1- _C14 (155)
1-C ₄ (115) 600
134 - - - 21 5N A (6.0) 1000 1- _C14 (155)
1-C ₄ (125) 300
98 - - - 6 5P A (7.2) 1000 1- _C14 (155)
1-C ₈ (143) 600 25

41 - - - -6 5Q A (6.0) 1000 1- _C14 (78)
1-C ₈ (215) 600 25

50 - - - 6 5R A (6.0) 1000 1- _C14 (39)
1-C ₈ (250) 600 25 - - - 0 5S A (6.0) 1000 1-C ₁₄ (271)
1-C ₈ (36) 600 25

55 - M _n = 10200
M _w = 24300 469 -11 5T A (6.0) 1000 1-C ₁₄ (271)
1-C ₈ (36) 600 25

44 - M _n = 11700
M _w = 20500 - -3 5U A (6.0) 1000 1-C ₁₄ (271)
1-C ₈ (36) 1000 25

43 - M _n = 12900
M _w = 20800 - -9 ^A C ₈ , 1-octene; C ₁₀ , 1-decene; C ₁₂ , 1-dodecene; C ₁₄ , 1-tetradecene.

Example 6

Process for the preparation of high -viscosity polyalphaolefins (PAO) using a combination of metallocene and chemically treated solid oxide ( SSA ) activators

High-viscosity alpha olefin homo oligomers and co-oligomers (PAO) can be prepared using the various metallocenes and chemically treated solid oxides (solid superacids, SSA) as catalyst system components, with reference to the oligomerization operation shown in Table 3 Was prepared according to the general method.

The metallocene indicated in Table 3 was dissolved or slurried in alpha olefin and then TIBA (1M solution in hexane) was added at room temperature. The mixture was stirred at room temperature for about 2 minutes. A chemically treated solid oxide (SSA) was added to the mixture, and the resulting mixture was stirred at room temperature for the indicated time, after which the oligomerization reaction was stopped. The reactions were strongly exothermic. In some instances, the quenched product is filtered and distilled to remove unreacted monomers and some lower oligomers with overhead fractions. Distillation was carried out at 210 ° C, from 0.1 torr to 1 torr, until no overhead product was recovered and for an additional hour.

^A fSSA, fluorinated silica-alumina

^B on-night

The conversion to oligomers measured by ^C gas chromatography

^D Distillation oligomer yield.

Example 7

1 - octene prepared using metallocene and chemically treated solid oxide combinations Oligomerization the viscosity and pour point by adjusting the temperature of the poly alpha olefin homo-oligomers (PAO)

1-octene homo-oligomer (PAO) was prepared by reacting 360 g 1-octene with 12.6 mg metallocene L, 1.03 g fluorinated silica-alumina (f-SSA), and 850 mg triisobutyl aluminum catalyst system at an oligomerization time of 16 &Lt; / RTI &gt; for hours. This example shows that a surprising variety of oligomer products are possible with varying oligomerization temperature. The results are shown in Table 4 . These batch operations show that the product viscosity can be controlled by temperature alone and that the same catalyst system can be used to produce high values of 100 cSt and / or 40 cSt.

These PAO product pour points are good compared to the commercially available product (ExxonMobil SpectraSyn 100) listed in the last column for comparison purposes.

Oligomerization and oligomer data for polyalphaolefins (PAO) prepared at various temperatures using metallocene and SSA activators. Examples ^{A, B} 7A 7B 7C 7D The commercially available PAO Oligomerization temperature 70 ℃ 80 ℃ 90 ° C 100 ℃ n.a. 100 C Visc. (cSt) 157 109 72 24 100 40 C Visc. (cSt) 1270 901 605 156 1240 Viscosity index 242 221 199 187 170 Pour Point (℃) -48 -48 -48 -63 -30 Conversion Rate (%) 88 88 77 98 n.a.

Example 8

Laboratory scale synthesis method for olefin oligomer preparation

Several olefin oligomers were prepared on a laboratory scale using the following general procedures. These oligomers were distilled and hydrogenated to produce PAO. Depending on the particular catalysts and conditions, this general procedure was applied to the preparation of olefin oligomers that were distilled and hydrogenated to provide PAO having 100 &lt; 0 &gt; C kinematic viscosity near 40 cSt and 100 cSt. Specific metallocene and oligomerization conditions and hydrogenated oligomer characterization data for each run are provided in Table 5. &lt; tb &gt;&lt; TABLE &gt; Where necessary or required, a few variations on the detailed procedure of this embodiment are possible. For example, some metallocenes may be added as slurries in 1-octene due to their low solubility. Each embodiment of Table 2 includes reference to patent drawings formed from this embodiment.

Oligomerization  step

The 18-L multi-neck flask was fitted with a heating mantle, an overhead stirrer, and a solid input funnel filled with fluorinated silica-alumina (f-SSA prepared as described herein). The flask was purged with nitrogen and was completely dried by washing with tri-isobutylaluminum (TIBA). Washing After removal of TIBA, anhydrous olefin was charged to the flask via tubing. The olefin was heated to the reaction temperature. Tri-isobutylaluminum (TIBA) was added to the flask, followed by metallocene dissolved in a very small amount of olefin. The total content of f-SSA was added and stirred to produce an exothermic reaction. The reaction mixture is heated (or cooled) to the desired reaction temperature and maintained at the desired reaction temperature for the desired reaction time. After the reaction time, the reaction mixture was analyzed by gas chromatography. The gas chromatographic analysis results are shown in Table 5. Alkylaluminates are neutralized with stoichiometric amounts of water (for example, 1 mole of water per mole of alkyl aluminum bond - about 3: 1 water: trialkyl aluminum). The product was filtered, distilled, and hydrogenated. The final hydrogenation product properties are reported in Table 5 .

Oligomerization  Procedure B

The 18-L multi-neck flask was fitted with a heating mantel, an overhead stirrer, and a solid input funnel with fluorinated silica-alumina (f-SSA). The flask was purged with nitrogen and was completely dried by washing with tri-isobutylaluminum (TIBA). Washing After removal of TIBA, anhydrous olefin was charged to the flask via tubing. The olefin was heated to the reaction temperature. When the reaction flask contents reached the reaction concentration, tri-isobutyl aluminum (TIBA) was added to the reaction flask. After stirring continuously for a period of typically 5-30 minutes for a few minutes, the metallocene (dissolved in a very small amount of olefin) and f-SSA were simultaneously introduced into the reaction flask and exothermic reaction occurred. The reaction mixture is heated (or cooled) to the desired reaction temperature and maintained at the desired reaction temperature for the desired reaction time. After the reaction time, the reaction mixture was analyzed by gas chromatography. The gas chromatographic analysis results are shown in Table 5. The alkylaluminates were neutralized with stoichiometric amounts of water. The product was filtered, distilled, and hydrogenated. The final hydrogenation product properties are reported in Table 5 .

Example 9

PAO Blend

PAO blends having kinematic viscosity of 35.0 cSt, 38.8 cSt, and 100 cSt at 100 占 폚 were prepared by mixing the PAOs produced in Example 8 operation. These PAO blends are shown in Table 6.

Blend B-1 was prepared by mixing the hydrogenated oligomers of Example 8-Run 2, Example 8-Run 3, and Example 8-Run 4 in the amounts shown in Table 6. Blend B-2 was prepared to have a 100 占 폚 kinematic viscosity near 40 cSt (actual 38.8) by blending the hydrogenated oligomers of Blend B-1 and Example 8-Run 8 in the amounts shown in Table 6. Blend B-3 was prepared to have a 100 ° C kinematic viscosity near 100 cSt (actual 99.3) by blending the hydrogenated oligomers of Blend B-2 and Example 8-Run 9 in the amounts shown in Table 6.

PAO blends Blend number Blend  B-1 Blend  B-2 Blend  B-3 Explanation Blend near 40 cSt Blend near 100 cSt Blend 42 wt% Example 8 - Operation 2
38% by weight Example 8 - Operation 3
20 wt% Example 8 - Operation 4 92 wt% Blend B-1
8 wt% Example 8 Operation 8 74.5 wt% Example 8 Operation 9
25.5 wt% B-2 100 C Visc, cSt 35.0 38.8 99.3 40 C Visc, cSt 280.9 318.6 992.5 Pour point, ℃ -53 -53 -42 Viscosity Index, VI 172 173 193

Table 7 compares the physical and chemical properties of the hydrogenated 1-octene oligomers of PAO Blend B-2 and PAO Blend B- 3 reported in Table 6 with the commercially available PAO 40 and PAO 100 produced from 1-decene.

PAO blends near 40 cSt B2 and PAO blends near 100 cSt B-3 and a comparison of commercially available PAO 40 and PAO 100 Physical Characteristics Commercially available
PAO 40 PAO
Blend B-2 Commercially available
PAO 100 PAO
Blend B-3 Viscosity, Kinematic 100 ° C (212 ° F) 40 38.8 100 99.3 Viscosity, copper 40 ° C (104 ° F) 395 319 1231 1014 -8 캜 Brookfield viscosity (cP) 12,150 6,566 51,403 28,435 -20 캜 Brookfield viscosity (cP) 45,465 20,025 Can not be measured with polar viscosity Can not be measured with polar viscosity -26 캜 Brookfield viscosity (cP) 102,000 35,524 - - Viscosity index 147 173 167 191 Pour Point, ℃ (℉) -36 -53 -30 -42 Flash Point (COC), ℃ (℉) 281 246 283 281 (COC), &lt; RTI ID = 0.0 &gt; 318 287 330 330 Volatile, noh, weight% 2.5 - 2.3 - DSC crystallization none none Yes, -40 ° C none importance 0.850 0.838 0.853 0.845 Exterior Transparent & Bright Transparent & Bright Transparent & Bright Transparent & Bright smell NFO ^A NFO ^A NFO ^A NFO ^A RPVOT, (min) 1976 2375 1621 2943 Stereochemistry diagram by ¹³ C NMR (catalyst) Cr-Si Metallocene based catalyst systems Cr-Si Metallocene based catalyst systems mm 29.6% 32.6% 25.1% 40.6% mr 42.7% 45.1% 34.5% 44.9% rr 27.7% 22.3% 40.4% 14.5% ^A nothing.

Table 7 Comparison As can be seen from the data, the 1-octene in the resulting PAO blends B-2 and B-3 PAO blend is lower than 40 PAO and PAO 100 is a commercially available 1-decene produced by the same temperature It has dynamic viscosity. This tendency is also reflected in the lower pour point and higher viscosity index of 1-octene-produced PAO blend B-2 and PAO blend B- 3 compared to commercially available PAO 40 and PAO 100 produced with 1-decene . The 1-octene-produced PAO blend B-2 has a lower flash point and an ignition point than the commercially available PAO 40 produced by 1-decene, whereas the 1-octene-produced PAO blend B- It has a flash point and an ignition point almost equal to that of the commercially available PAO 100 produced. PAO blend B-2 and PAO blend B-3 produced with 1-octene have lower NOACK volatility (ASTM D-5800) than commercially available PAO 40 and PAO 100 produced with 1-decene. Lower furnace volatility has lower evaporation loss, more useful wear resistance, reduced emission in the high temperature service of PAO blend B-2 and PAO blend B- 3 produced with 1-octene versus commercially available PAO 40 and 100 with similar kinematic viscosity , Reduced oil consumption, and improved fuel economy. As discussed, RPVOT data show higher oxidation stability of PAO blend B-2 and PAO blend B- 3 produced with 1-octene versus commercially available PAOs having similar kinematic viscosity.

The change in kinematic viscosity (cP) as a function of temperature (° C) of PAO blend B-2 and PAO blend B- 3 produced with 1-octene was compared with PAO having similar kinetic constants commercially available. For example, Figure 1 shows the kinetic viscosity (cP) versus temperature (占 폚) of 1-octene produced PAO blend B-2 made according to the present invention and comparable commercially available PAO 40 having similar kinematic viscosity, FIG. Similarly, Figure 2 shows the kinematic viscosity (cP) versus temperature (C) plot of the 1-octene-produced PAO blend B-2 produced by the present invention and comparable commercially available PAO 100 with similar kinematic viscosity FIG. The data limit for the commercially available PAO 100 ( A line) is the result of reaching the acoustic transducer torque limit of the Brookfield viscometer. In each case, the 1-octene-produced PAO blend B-2 and the PAO blend B-3 have lower kinematic viscosities, such as PAO having similar commercially available kinetic constants produced by 1-decene.

Figure 3 provides RPVOT (Rotary Pressure Vessel Oxidation Experiment) analysis results for the oxidation stability of various PAOs measured according to ASTM D2272. Oxidation stability plots of oxygen pressure (psig) versus time (min) are shown for PAO blend B-2 and PAO blend B-3 made from 1-octene using metallocene and chemically treated solid oxide catalyst systems, Lt; RTI ID = 0.0 &gt; 100 C &lt; / RTI &gt; Sample classification: A , PAO blend B-2; B , Example 8 - Operation 8, hydrogenated 1-octene oligomer hydrogenated at 210 占 폚; C , Example 8 - Operation 8, hydrogenated 1-octene oligomer hydrogenated at 165 占 폚; D , commercially available PAO 40; E , commercially available PAO 100. A Line to D line shows a comparison between PAO produced using the catalyst system and / or method of the present invention and PAO having a similar commercially available 100 ° C kinematic viscosity. The B line and C line, versus E line show a comparison between PAO produced using the catalyst system and / or method of the present invention and PAO having a similar commercially available 100 ° C kinematic viscosity.

Figure 3 RPVOT experiments were carried out in the presence of 0.5% Naugalube APAN (alkylated phenyl- alpha -naphthylamine) antioxidant as standard antioxidant concentration. Rapid oxygen pressure losses in nearly vertical portions of each curve correspond to antioxidant depletion and rapid sample oxidation. Above all, this figure shows a substantially higher oxidation stability of the PAO produced by the catalyst system and / or process of the present invention compared to PAO having a similar or corresponding kinematic viscosity, commercially available.

Figure 4 shows the metallocene effect of the catalyst system on the kinematic viscosity of PAO produced using the catalyst system and / or method of the present invention. Thus, Figure 4 shows the kinematic viscosity (cP) versus temperature (占 폚) of a series of PAOs having similar 100 占 폚 kinematic viscosity produced using different metallocene catalyst systems, and the commercially available 40 cSt polyalphaolefin The dynamic viscosity is compared with the behavior. 4 samples are as follows: A , Example 8 - Run 5; B , Example 8 - Operation 6; C , Example 8 - Operation 7; D , commercially available PAO 40; E , PAO blend B-2 . See Table 6 and 7 for sample preparation and characteristics. Similarly, Figure 5 shows the kinematic viscosity (cP) versus temperature (C) of a series of PAOs having similar 100 &lt; 0 &gt; C kinetic constants produced using different metallocene catalyst systems, and commercially available PAO 100 cSt polyalpha The dynamic viscosity behavior of olefins is compared with the behavior. 5 samples are as follows: A , Example 8 - Run 10; B , Example 8 - Operation 11; C , Example 8 - Operation 12; D , commercially available PAO 100. See Tables 6 and 7 for sample preparation and characteristics.

Example 10

One- Hexen  And / or To Dodesen  Generated Polyalphaolefin  ( PAO )

The olefinic oligomeric polyalphaolefins (PAO) resulting from 1-hexene and 1-dodecene were similarly prepared according to the general procedure outlined in Examples 8 and 9. Selected reaction conditions and homo oligomer properties are shown in Table 8 .

Preparation and properties of 1-hexene and 1-dodecene olefin oligomers (non-hydrogenated) Driving number 10-A 10-B 10-C Olefin 1-hexene 1-hexene 1-dodecene Olefin feed, mL 500 500 500 Metallocene K G C Activator f-SSA f-SSA MMAO Activator, g or mole ratio 2.06 0.260 1000: 1 Al: Zr TIBA, g 1.7 0.220 0 Yield (distillation), g - 263 - Temperature, ℃ 60 60 25 Temperature, maximum. ℃ 65 - 40 Conversion to oligomer, weight% - 78% - 100 ° C Kinematic viscosity, cSt 228 197.4 437 40 ℃ Kinematic viscosity, cSt 4348 3545 4445 Pour point, ℃ -42 -24 -25 Viscosity index 170 168 279

Example 11

Bis (ethylcyclopentadienyl) zirconium The polyalphaolefins produced using the 2-chloride / f- SSA catalyst system .

A multi-well flask of the appropriate size was mounted in a solids input funnel containing a heating mantle, an overhead stirrer, and fluorinated silica-alumina (f-SSA). The flask was purged with nitrogen and completely dried with TIBA pre-wash. Olefins were charged to the flask via tubing. The olefin was heated to the reaction temperature. When the contents of the flask reached the desired reaction temperature, the alkyl aluminum compound was added to the reaction flask. After continued stirring for several minutes, bis (ethylcyclopentadienyl) zirconium dichloride dissolved in a very small amount of olefin, typically for 5 to 30 minutes, was exothermic when put into the reactor simultaneously with f-SSA. The flask contents were cooled to the desired reaction temperature and the reaction temperature was maintained preferably overnight (about 16 hours) using heating mantles. After the reaction time was complete, the reaction was quenched with a stoichiometric amount of water to neutralize the alkyl aluminum. The product was filtered, distilled, and hydrogenated according to the procedure set forth in Example 8. Table 9 provides information on oligomerization operations and hydrogenated oligomer properties. The operation using an alumoxane MMAO requires more metallocene than the oligomerization using f-SSA as an activator.

Example 12

100 ℃ Kinematic viscosity  About 40 cS Polyalphaolefin  Test factory method for manufacturing

Several batches of 1-octene oligomers having a 100 &lt; 0 &gt; C kinematic viscosity of about 40 cSt when distilled and hydrogenated were prepared according to the following procedure. The oligomerization data for each oligomerization reaction batch is shown in Table 10.

In a dry nitrogen atmosphere, a 1,000-pound dry 1-octene (dry with active AZ-300 alumina) sample was charged to a pre-dried test plant batch reactor by contact with tri-isobutyl aluminum (TIBA). The 1-octene sample was heated to 5 to 10 ° C lower than the desired reaction temperature with stirring. To the reactor was added a 10% solution of triisobutylaluminum in hexane. The mixture was stirred for 20 minutes and then a solution of fluorinated silica-alumina (f-SSA) and (η ⁵ -n-BuCp) ₂ ZrCl ₂ (compound H ) TIBA mixture. Exotherm was observed and then the reaction mixture was adjusted to the desired reaction temperature for a desired period of time (when the 1-octene conversion to tetrameric or higher oligomers, as judged by gas chromatography, is typically in the range of about 60% -75%). After this time, the reaction mixture was cooled to about 50 &lt; 0 &gt; C. The reaction mixture was transferred to a catalytically active tank where the catalyst composition was inert with water, typically about 4 ounces of water. The inert oligomer mixture was stirred for at least one hour and the oligomer mixture was cooled to ambient temperature. The inert reaction mixture was filtered to remove the inert catalyst system. Specific reaction information for each oligomerization configuration is shown in Table 10 .

The inert and filtered oligomerization product mixture was transferred to one or both of the distillation constituents and vacuum distilled to remove most of the unreacted monomers and the top dimer. The distillation bottoms were kept in the drum. Table 11 provides information on the distillation reaction of each of the 1-octene oligomerization batches.

 Various amounts of distilled oligomer products were hydrogenated to the reactor with about 60 pounds of supported nickel catalyst (HTC NI 500 RP, available from Johnson Matthey) to hydrogenate the distillation oligomers. The oligomer was hydrogenated at about 180 ° C and 430 psig to 500 psig hydrogen to a bromine index of less than 200. The hydrogenation product was filtered to remove the hydrogenation catalyst and stored in a drum. Table 12 provides information on the specific distillation oligomer batch content and hydrogenated oligomer batch characteristics applied in each hydrogenation operation. Table 1 is a flow chart showing oligomerization (O), distillation (D), and hydrogenation (H) flow through the oligomer.

Test plant oligomerization data for the olefin oligomers of Example 12 Oligomerization operation number O-1 O-2 O-3 O-4 O-5 1-octene (lbs) 1000 1000 1000 1000 1000 Triisobutylaluminum (lbs 10% by weight, solution) 9.3 9.2 9.25 9.2 9.35 (? ^5- n-BuCp) ₂ ZrCl ₂ (gram) 5.8 5.8 5.8 5.8 5.8 f-SSA (lbs) 4.1 3.92 3.88 4.1 4.0 (η ⁵ -n-BuCp) ₂ ZrCl ₂ addition temperature (° C.) 101 102 100 99 100 Maximum heat temperature (℃) 111 111 108 110 110 Oligomerization temperature (占 폚) 105 108 108 110 110 Oligomerization time (hours) 4.75 4.5 7.2 4.0 4.7 Total Conversion Rate, End of Process (%) 74.25 74.37 73.48 72.08 69.99 Monomer (%) 9.46 5.87 9.32 7.25 4.36 Dimer (%) 11.86 14.16 11.84 14.59 17.99 Trimer (%) 4.43 5.60 5.36 6.08 7.66 ^{The †} conversion is the 1-octene percent converted to the tetrameric or higher heavy oligomer.

Hydrogenation data for the distillation oligomers D-1a, D-1b, D-2, D-3a, D-3b, D-4, D-5a, D-5b, D-5c and D- Hydrogenation number H-1 H-2 H-3 H-4 Distillation batch charge for hydrogenation (lbs.) D-1a (162.6)
D-lb (606.8)
D-3b (273.1) D-2 (422.4)
D-3a (308.0)
D-3b &lt; / RTI &gt; (213.4)
D-4,5d (85.0) D-2 (116)
D-4a &lt; / RTI &gt; (299)
D-4,5d (456.8) D-4, 5b (496.2)
D-4,5c (296.6) Hydrogenated PAO content (lbs.) 861 918.2 833.4 700 100 ° C Viscosity (cSt) 42.1 36.9 33.573 34.345

Table 1. Sample flow through oligomerization (O), distillation (D), hydrogenation (H), and blend (B).

Example 13

Nominally 100 cSt Polyalphaolefin  ( HVPAO Test factory method for manufacturing

Several batches of 1-octene oligomers having a 100 &lt; 0 &gt; C kinematic viscosity of about 100 cSt when distilled and hydrogenated were prepared according to the following procedure. The oligomerization data for each oligomerization reaction batch is shown in Table 13. [

In a dry nitrogen atmosphere, a 1,000-pound dry 1-octene (dry with active AZ-300 alumina) sample was charged to a pre-dried test plant batch reactor by contact with tri-isobutyl aluminum (TIBA). The 1-octene sample was heated to 5 to 10 ° C lower than the desired reaction temperature with stirring. To the reactor was added a 10% solution of tri-isobutylaluminum (in hexane). After the mixture was stirred for 20 minutes, the fluorinated silica-alumina (f-SSA) powder and (η ⁵ -n-BuCp) ₂ ZrCl ₂ (compound H ) dissolved in a very small amount of 1-octene were mixed with 1-octene- Was added to the mixture. Exotherm was observed and then the reaction mixture was adjusted to the desired reaction temperature for a desired period of time (when the 1-octene conversion to tetrameric or higher oligomers, as judged by gas chromatography, is typically in the range of about 60% -75%). After this time, the reaction mixture was cooled to about 50 &lt; 0 &gt; C. The reaction mixture was transferred to a catalytically active tank where the catalyst composition was inert with water, typically about 4 ounces of water. The inert oligomer mixture was stirred for at least one hour and the oligomer mixture was cooled to ambient temperature. The inert reaction mixture was filtered to remove the inert catalyst system. Specific reaction information for each oligomerization configuration is shown in Table 13 .

Test factory oligomerization data for the olefin oligomers of Example 13 Oligomerization operation number O-6 O-7 O-8 O-9 O-10 1-octene (lbs) 1000 1000 1000 1000 1000 Triisobutylaluminum (lbs 10% by weight, solution) 10.3 9.2 9.2 9.3 9.2 (? ^5- n-BuCp) ₂ ZrCl ₂ (gram) 5.8 5.8 5.8 5.8 5.8 f-SSA (lbs) 4.06 3.84 3.88 4.02 3.52 (η ⁵ -n-BuCp) ₂ ZrCl ₂ addition temperature (° C.) 85 81 79 80 81 Maximum heat temperature (℃) 88 89 87 86 86 Oligomerization temperature (占 폚) 88 85 86 85 86 Oligomerization time (hours) 4.12 7.9 8.72 5.3 7.33 Total Conversion Rate, End of Process (%) 60.7 85.8 78.8 84.2 84.1 Monomer (%) 27.4 6.2 10.0 8.9 7.3 Dimer (%) 9.3 5.8 8.6 5.0 6.4 Trimer (%) 2.6 2.2 2.6 1.9 2.2 ^{The †} conversion is the 1-octene percent converted to the tetrameric or higher heavy oligomer.

The inert and filtered oligomerization product mixture was transferred to one or both of the distillation constituents and vacuum distilled to remove most of the unreacted monomers and the top dimer. The distillation bottoms were kept in the drum. Table 14 provides information on the distillation reactants of each of the 1-octene oligomerization batches

Various amounts of distilled oligomer products were hydrogenated to the reactor with about 60 pounds of supported nickel catalyst (HTC NI 500 RP, available from Johnson Matthey) to hydrogenate the distillation oligomers. The oligomer was hydrogenated at about 180 ° C and 420 psig to 440 psig of hydrogen. The hydrogenation product was filtered to remove the hydrogenation catalyst and stored in a drum. Table 15 provides information on the specific distillation oligomer batch content and hydrogenated oligomer batch characteristics applied in each hydrogenation operation.

Hydrogenation data for the olefin oligomer of Example 13 Hydrogenation number H-5 H-6 H-7 H-8 Distillation batch charge for hydrogenation (lbs.) D-6 (332.2)
D-7 (476.2)
D-8 (216.6) D-8 (406.0)
D-9 (332.4)
D-10 (61.6) D-10 (499.2)
D-11 (353.2) D-11 (225.0)
D-12 (585.4) Hydrogenated PAO content (lbs.) 882.8 900.0 852.4 810.4 100 ° C Viscosity (cSt) 115 134.9 149.5 140.4 40 ℃ Viscosity (cSt) 1204 1430 1618 1504 Viscosity index 195 201 204 202 Pour Point (℃) -42 - - - Flash point (℃) 266 - - - Ignition point (℃) 300 - - -

Example 14

One- Octen  The resulting different viscosity PAO's  mix

The hydrogenated oligomers produced in Examples 12 and 13 were mixed to produce PAO having a kinematic viscosity at 100 ° C of about 40 cSt or 100 cSt. Table 16 provides information on the mixed hydrogenated oligomer (PAO) notation and content and the final properties of the PAO blend.

The blend data for the hydrogenated 1-octene oligomer produced in Example 12 Blend number B-4 B-5 Hydrogenated PAO source (lbs.) H-1 (854.2)
H-2 (715.8)
H-3 (94.8)
H-4 (105.6)
H-5 (59.2) B-4 (29.6)
H-4 (93)
H-5 (817.8) 100 ° C Viscosity (cSt) 40.1 100.6 40 ℃ Viscosity (cSt) 342.3 1007 Viscosity index 169.7 193

Example 15

Method pilot plant for producing polyalphaolefin having a kinematic viscosity of about 100 cS 100 ℃

In a dry nitrogen atmosphere, a 994-pound dry 1-octene (dry with active AZ-300 alumina) sample was charged to a pre-dried test plant batch reactor by contact with tri-isobutyl aluminum (TIBA). The 1-octene sample was heated to 70 DEG C with stirring. The reactor was charged with 4.4 lbs of a 10% solution of triisobutylaluminum in hexane (lbs TIBA) and 2.7 lbs of a 12.6% solution of triisobutylaluminum in hexane. After stirring the mixture for 5 minutes, 717 grams of fluorinated silica-alumina (f-SSA) powder and 1.2 grams of (η ⁵ -n-ethyl Cp) ₂ ZrCl ₂ (Compound P) dissolved in a very small amount of 1-octene Lt; RTI ID = 0.0 &gt; 1-octene / TIBA &lt; / RTI &gt; An exotherm was observed, after which the reaction mixture was adjusted to 75 DEG C for 8.33 hours. The reaction mixture was cooled to about 50 &lt; 0 &gt; C. The reaction mixture was transferred to a catalytically active tank where the catalyst composition was inert with water, typically about 4 ounces of water. The inert oligomer mixture was stirred for at least one hour and the oligomer mixture was cooled to ambient temperature. The inert reaction mixture was filtered to remove the inert catalyst system. Reactor effluent GC analysis confirmed that 14.1 wt% monomer, 7.6 wt% dimer, and 2.3 wt% trimer were included. The conversion of 1-octene to the heavy oligomer was therefore 76%.

The inert and filtered oligomerization product mixture was transferred to a distillation apparatus-apparatus and vacuum distilled to remove most unreacted monomers and top dimers. The distillation bottoms were kept in the drum. Hydrogenation reactor effluent GC analysis confirmed that the distillation oligomers contained 0 wt% monomer, 0.6 wt% dimer, 3.2 wt% trimer, and 96.2 wt% heavy oligomer. Also, the distillation oligomer analysis confirmed that the distillation oligomer had a kinematic viscosity at 100 ° C of 97.4 cSt.

The distillation oligomers were hydrogenated by charging 530.4 lbs of distilled oligomer product with about 80 pounds of supported nickel catalyst (HTC NI 500 RP, available from Johnson Matthey) in the reactor. The oligomer was hydrogenated at about 180 ° C and 440 psig of hydrogen. The hydrogenation product was filtered to remove the hydrogenation catalyst and stored in a drum. From the analysis of the distillation oligomer, it was confirmed that the distillation oligomer had a kinematic viscosity at 105 ° CSt at 100 ° C, a kinematic viscosity at 106 ° CSt at 40 ° C, and a viscosity index of 194.

Example 16

Adjustment of PAO Viscosity and Pour Point by Oligomerization Temperature for 1- Octene Homo Oligomer ( PAO )

Using the metallocene L (below) in combination with fluorinated silica-alumina (f-SSA), according to the general procedure of Examples 8 or 9, with each run of the different reaction temperatures, 1-octene homo oligomer (PAO ). The results of these operations are shown in Table 17.

Compound L

Each oligomerization operation was conducted with 360 g of 1-octene, 12.6 mg of metallocene compound F , 850 mg of TIBAL (triisobutylaluminum), 1.03 g of solid f-SSA, and a 16- . The same metallocene-activator-support catalyst system was used and only the oligomerization temperature was varied to produce a wide variety of PAO products, which are summarized in Table 18. These batch operations can control the PAO product viscosity in this metallocene / SSA catalyst system and method at temperature only and produce an oligomer distribution which, when hydrogenated, can provide 100 cSt and / or 40 cSt PAO without blending . As shown in Table 17 , the product pour point is lower than the commercially available PAO 40 and PAO 100.

Oligomerization and oligomerization of polyalphaolefins (PAO) from 1-octene using the same metallocene and activator at various temperatures Driving number One 2 3 4 Commercially available
100 Commercially available
40 Oligomerization temperature 80 ℃ 90 ° C 100 ℃ 110 ° C - - 100 ° C viscosity, cSt 172 93 37 10 100 39 40 ° C viscosity, cSt 1773 873 277 150 1240 396 Viscosity Index (VI) 217 197 175 193 170 147 Pour Point (℃) -42 -42 -57 -76 -30 -36 Conversion to oligomer (%) 88 77 98 98 n.a. n.a.

Example 17

The Polyalphaolefin  ( PAO Other for Metallocene  Catalyst system

As the present disclosure, some additional representative, non-limiting, exemplary, specific, metallocene-based catalyst systems are shown in Table 18. These combinations can be used in accordance with embodiments and generally in accordance with the present invention, and are provided in non-limiting combinations.

Exemplary specific metallocene-based catalyst systems for making the PAOs of the present invention Example  number Metallocene Solid oxide activator Co-catalyst and / or Alkyl  aluminum ^A 17-B

Fluorinated silica-alumina (f-SSA), chlorinated alumina, or sulfated alumina TIBA, TEA, TMA, MAO, MMAO, or TBA 17-D

Fluorinated silica-alumina (f-SSA), chlorinated alumina, or sulfated alumina TIBA, TEA, TMA, MAO, MMAO, or TBA 17-I

Fluorinated silica-alumina (f-SSA), chlorinated alumina, or sulfated alumina TIBA, TEA, TMA, MAO, MMAO, or TBA 17-J

Fluorinated silica-alumina (f-SSA), chlorinated alumina, or sulfated alumina TIBA, TEA, TMA, MAO, MMAO, or TBA 17-L

Fluorinated silica-alumina (f-SSA), chlorinated alumina, or sulfated alumina TIBA, TEA, TMA, MAO, MMAO, or TBA 17-M

Fluorinated silica-alumina (f-SSA), chlorinated alumina, or sulfated alumina TIBA, TEA, TMA, MAO, MMAO, or TBA 17-N

Fluorinated silica-alumina (f-SSA), chlorinated alumina, or sulfated alumina TIBA, TEA, TMA, MAO, MMAO, or TBA 17-O

Fluorinated silica-alumina (f-SSA), chlorinated alumina, or sulfated alumina TIBA, TEA, TMA, MAO, MMAO, or TBA 17-P

Fluorinated silica-alumina (f-SSA), chlorinated alumina, or sulfated alumina TIBA, TEA, TMA, MAO, MMAO, or TBA 17-U

Fluorinated silica-alumina (f-SSA), chlorinated alumina, or sulfated alumina TIBA, TEA, TMA, MAO, MMAO, or TBA 17-V

Fluorinated silica-alumina (f-SSA), chlorinated alumina, or sulfated alumina TIBA, TEA, TMA, MAO, MMAO, or TBA 17-W

Fluorinated silica-alumina (f-SSA), chlorinated alumina, or sulfated alumina TIBA, TEA, TMA, MAO, MMAO, or TBA 17-X

Fluorinated silica-alumina (f-SSA), chlorinated alumina, or sulfated alumina TIBA, TEA, TMA, MAO, MMAO, or TBA 17-Y

Fluorinated silica-alumina (f-SSA), chlorinated alumina, or sulfated alumina TIBA, TEA, TMA, MAO, MMAO, or TBA ^A Abbreviations: TIBA, triisobutylaluminum; TEA, triethylaluminum; TMA, trimethyl aluminum; MAO, methyl aluminoxane; MMAO, isobutyl-modified methylaluminoxane; TBA, tri-n-butyl aluminum

Claims (20)

comprising the steps of: a) contacting a C ₄ to C ₂₀ alpha olefin monomer with a catalyst system,
1) metallocenes,
2) a first activator comprising a solid-oxide chemically-treated with an electron attracting anion, and
3) a second activator comprising an organoaluminum compound having the formula Al (X ¹⁰ ) _n (X ¹¹ ) _{3 - n} , wherein X ¹⁰ is independently C ₁ to C ₂₀ hydrocarbyl and X ¹¹ is Independently is a halide, a hydride, or a C ₁ to C ₂₀ hydrocarboxylide, and n is a number from 1 to 3; and
b) forming an oligomeric product under oligomerization conditions. 2. The method of claim 1, wherein the solid oxide chemically-treated with the electron attracting anion comprises a fluorinated solid oxide. 2. The method of claim 1, wherein the solid oxide chemically-treated with the electron attracting anion comprises a sulfurated solid oxide. The method of claim 1, wherein the second activator comprises a trialkyl aluminum, an alkyl aluminum sesquihalide, an alkyl aluminum halide, or any combination thereof. The method according to claim 1,
Wherein the alpha olefin monomer comprises a C ₆ to C ₁₆ normal alpha olefin;
Wherein the solid oxide chemically treated with the electron attracting anion comprises fluorinated alumina, chlorinated alumina, sulfated alumina, fluorinated silica-alumina, or any combination thereof;
Wherein the second activator comprises trialkyl aluminum. The method according to claim 1,
Wherein the molar ratio of aluminum in the organoaluminum compound to the metal (Al: metal) in the metallocene ranges from 1: 1 to 10,000: 1;
The first activator to metallocene weight ratio range is from 1: 1 to 100,000: 1; And
Wherein the alpha olefin monomer to metallocene weight ratio range is from 100: 1 to 10,000, 000: 1. The process of claim 1, wherein the alpha olefin monomer and the catalyst system comprise:
(1) contacting the alpha olefin monomer with the second activator to form a mixture; And
(2) contacting said mixture with said first activator and said metallocene in any order. The method according to claim 1,
The oligomerization conditions include a temperature range of from 50 캜 to 165 캜;
At least 80% by weight of said alpha olefin monomer is converted to said oligomer product;
Wherein the oligomeric product comprises dimer, trimer, and even higher oligomer, wherein the oligomeric product comprises at least 75 wt% heavy oligomer. 9. The method of claim 8, further comprising separating the oligomerization reactor effluent comprising the oligomer product to provide a product of a heavy oligomer, wherein at least a portion of the alpha olefin monomer, dimer, or trimer is oligomerized Lt; RTI ID = 0.0 &gt; oligomerization &lt; / RTI &gt; product. 10. The composition of claim 9, wherein the heavy oligomer product comprises less than 0.2 weight percent alpha olefin monomer, less than 0.5 weight percent dimer, and at least 88 weight percent still higher oligomer, based on the total weight of the heavy oligomer product and; And
Wherein the heavy oligomer product has a kinematic viscosity at 100 DEG C of from 15 cSt to 250 cSt. The method according to claim 1,
Wherein the metallocene has the formula (? ⁵ -cycloalkadienyl) ₂ M ³ X ⁹ ₂ ,
doedoe connected by a connecting group having a, R ^1, - i) Two (η ⁵ - cycloalkyl alkyne diene-yl) ligand ^{structure> CR 1 R 2,> SiR} 3 R 4, or -CR ⁵ R ⁶ CR ⁷ R ⁸ R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are independently selected from hydrogen or a saturated or unsaturated C ₁ -C ₂₀ hydrocarbyl group,
ii) each η ⁵ -cycloalkadienyl ligand is independently an optionally substituted or non-substituted cyclopentadienyl ligand, a substituted or non-substituted indanyl ligand, or a substituted or unsubstituted fluorenyl And each non-linking substituent is independently a halide, a C ₁ to C ₂₀ hydrocarbyl group, or a C ₁ to C ₂₀ hydrocarboxy group,
iii) X ⁹ is a halide, a C ₁ -C ₂₀ hydrocarbyl group, or a C ₁ -C ₂₀ hydrocarboxy group, and
iv) M is Zr and ^3;
Wherein the solid oxide chemically treated with the electron attracting anion comprises fluorinated alumina, chlorinated alumina, sulfated alumina, fluorinated silica-alumina, or any combination thereof;
Wherein the organoaluminum compound comprises a trialkyl aluminum, an alkyl aluminum sesquihalide, an alkyl aluminum halide, or any combination thereof;
The alpha olefin monomers and the catalyst system can be prepared,
i) the molar ratio of metal in the organoaluminum compound to metal (Al: metal) in the metallocene ranges from 50: 1 to 500: 1;
ii) the first activator to metallocene weight ratio ranges from 100: 1 to 1,000: 1; And
iii) the alpha olefin monomer to metallocene weight ratio ranges from 1,000: 1 to 10,000,000: 1;
The oligomerization conditions include a temperature range of from 50 캜 to 165 캜;
At least 80% by weight of said alpha olefin monomer is converted to said oligomer product; And
Wherein the oligomeric product comprises dimer, trimer, and even higher oligomer, wherein the oligomeric product comprises at least 75 wt% heavy oligomer. comprising the steps of: a) contacting a C ₄ to C ₂₀ alpha olefin monomer with a catalyst system,
1) metallocenes,
2) a first activator comprising a solid-oxide chemically-treated with an electron attracting anion, and
3) a second activator comprising an organoaluminum compound having the formula Al (X ¹⁰ ) _n (X ¹¹ ) _{3 - n} , wherein X ¹⁰ is independently C ₁ to C ₂₀ hydrocarbyl and X ¹¹ is Independently, a halide, a hydride, or a C ₁ to C ₂₀ hydrocarboxylate, and n is a number from 1 to 3;
b) forming an oligomeric product comprising dimer, trimer, and even higher order oligomer under oligomerization conditions;
c) separating the oligomerization reactor effluent comprising the oligomeric product to provide a product of a heavy oligomer, wherein at least a portion of the alpha olefin monomer, dimer, or trimer is removed from the oligomerization reactor effluent, Providing the heavy oligomer product, wherein the heavy oligomer product is formed; And
d) hydrogenating the heavy oligomer product to produce a polyalphaolefin. 13. The method of claim 12,
1) the alpha olefin monomer comprises a C ₆ to C ₁₆ normal alpha olefin;
2) The catalyst system comprises:
i) formula (η ⁵ - cyclo alkynyl diene yl) ₂ M ³ X ⁹ ₂ of the metallocene (wherein in the metal having,
(1) two (η ⁵ -cycloalkadienyl) ligands are connected by a linking group having the structure> CR ¹ R ² ,> SiR ³ R ⁴ , or -CR ⁵ R ⁶ CR ⁷ R ⁸ , wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are independently selected from hydrogen or a saturated or unsaturated C ₁ -C ₂₀ hydrocarbyl group,
(2) each η ⁵ -cycloalkadienyl ligand is independently a substituted or non-substituted cyclopentadienyl ligand, a substituted or non-substituted indanyl ligand, or a substituted or non-substituted fluorene Wherein each non-linking substituent is independently a halide, a C ₁ to C ₂₀ hydrocarbyl group, or a C ₁ to C ₂₀ hydrocarboxy group,
(3) X ⁹ is a halide, a C ₁ -C ₂₀ hydrocarbyl group, or a C ₁ -C ₂₀ hydroxycarboxyl group, and
(4) M &lt; ³ &gt; is Zr;
ii) the first activator comprising fluorinated alumina, chlorinated alumina, sulfated alumina, fluorinated silica-alumina, or any combination thereof;
iii) said second activator comprising a trialkyl aluminum, an alkyl aluminum sesquihalide, an alkyl aluminum halide, or any combination thereof;
3) The alpha olefin monomer and the catalyst system,
i) the molar ratio of metal in the organoaluminum compound to metal (Al: metal) in the metallocene ranges from 50: 1 to 500: 1;
ii) the first activator to metallocene weight ratio ranges from 100: 1 to 1,000: 1; And
iii) the alpha olefin to metallocene weight ratio ranges from 1,000: 1 to 10,000,000: 1;
4) the oligomerization conditions have a temperature range of from 50 ° C to 165 ° C;
5) The polyalphaolefin,
i) less than 0.5% by weight hydrogenated alpha olefin monomer,
ii) less than 1% by weight hydrogenated dimer, and
iii) at least 88% by weight hydrogenated heavy oligomer; And
6) The polyalphaolefin,
i) a kinematic viscosity at 100 占 폚 of 25 cSt to 225 cSt,
ii) the viscosity index exceeds 155,
iii) the pour point is less than -30 占 폚. 13. The method of claim 12,
1) the alpha olefin monomer comprises a C ₆ to C ₁₆ normal alpha olefin;
2) The catalyst system,
i)

,

,

,

Or a metallocene having any combination thereof,
(1) each of R ²⁰ , R ²¹ , R ²³ , and R ²⁴ is independently hydrogen, a C ₁ to C ₂₀ alkyl group, or a C ₂ to C ₁₀ alkenyl group, and
(2) each of X ¹² , X ¹³ , X ¹⁵ , and X ¹⁶ is independently F, Cl, Br, or I;
ii) the first activator comprising fluorinated alumina, chlorinated alumina, sulfated alumina, fluorinated silica-alumina, or any combination thereof, and
iii) said second activator comprising a trialkyl aluminum, an alkyl aluminum sesquihalide, an alkyl aluminum halide, or any combination thereof;
3) The alpha olefin monomer and the catalyst system,
i) the molar ratio of aluminum in the organoaluminum compound to the metal (Al: metal) in the metallocene ranges from 50: 1 to 500: 1,
ii) the first activator to metallocene weight ratio ranges from 100: 1 to 1,000: 1, and
iii) the alpha olefin to metallocene weight ratio ranges from 1,000: 1 to 10,000,000; And
4) The oligomerization condition is a temperature range of 90 ° C to 120 ° C. 13. The method of claim 12,
1) the alpha olefin monomer comprises a C ₆ to C ₁₆ normal alpha olefin;
2) The catalyst system,
i) the metallocene having the formula:

(Wherein,
(1) each R ²⁰ is independently hydrogen, a C ₁ to C ₁₀ alkyl group, or a C ₂ to C ₁₀ alkenyl group, and
(2) each X ¹² is independently Cl or Br);
ii) the first activator comprising fluorinated silica-alumina, and
iii) said second activator comprising trialkyl aluminum;
3) The alpha olefin monomer and the catalyst system,
i) the molar ratio of aluminum in the organoaluminum compound to the metal (Al: metal) in the metallocene ranges from 50: 1 to 500: 1,
ii) the first activator to metallocene weight ratio ranges from 100: 1 to 1,000: 1, and
iii) an alpha olefin to metallocene weight ratio of from 1,000: 1 to 10,000,000;
4) the oligomerization conditions have a temperature range of 70 ° C to 140 ° C;
5) The polyalphaolefin,
i) less than 0.5% by weight hydrogenated alpha olefin monomer,
ii) less than 1% by weight hydrogenated dimer, and
iii) at least 88% by weight hydrogenated heavy oligomer; And
6) The polyalphaolefin,
i) a kinematic viscosity at 100 占 폚 of 30 cSt to 140 cSt,
ii) the viscosity index exceeds 155,
iii) the pour point is less than -35 ° C, and
v) A method of producing a polyalphaolefin free from discernible crystallization as determined by differential scanning calorimetry using ASTM D 3418. 13. The method of claim 12, further comprising blending the polyalphaolefin with at least a second polyalphaolefin. 17. The method of claim 16,
a) the second polyalphaolefin has a kinematic viscosity at 100 DEG C of at least 10 cSt above the polyalphaolefin;
b) the second polyalphaolefin is produced using a different monomer than the polyalphaolefin; or
c) a process for producing a polyalphaolefin, wherein the second polyalphaolefin has a kinematic viscosity at 100 DEG C of at least 10 cSt with the polyalphaolefin and the second polyalphaolefin is produced using a different monomer than the polyalphaolefin . 13. The process according to claim 12, wherein the poly-alpha olefin has a Bernoulli index of less than 1.65. 13. The method of claim 12, wherein the polyalphaolefin is free of discernible crystallization as determined by differential scanning calorimetry using ASTM D 3418. The process for producing a polyalphaolefin according to claim 12, wherein the polyalphaolefin has a viscosity index of 170 to 220.

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